CN1321953C

CN1321953C - Reducing temperature differences within the regenerator of an oxygenate to olefin process

Info

Publication number: CN1321953C
Application number: CNB028275772A
Authority: CN
Inventors: 徐腾; P·N·奇斯霍姆; S·N·瓦格恩; S·C·方; K·H·库彻勒; J·R·拉特纳; K·R·克莱姆; P·J·马赫; D·C·德拉梅尔
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2002-01-07
Filing date: 2002-12-12
Publication date: 2007-06-20
Anticipated expiration: 2022-12-12
Also published as: US7053260B2; EP1461301A1; EA200400874A1; AU2002360559A1; MY129487A; EP1461301B1; TW200301775A; BR0215481A; TWI291989B; WO2003059850A1; EA007659B1; US20030163010A1; CN1617842A

Abstract

The present invention provides a process for making an olefin product from an oxygenate feedstock which comprises: a) contacting the feedstock in a reaction zone with a catalyst comprising i) a molecular sieve having defined pore openings and ii) a CO oxidation metal, under conditions effective to convert the feedstock into an olefin product stream comprising C2-C3 olefins and to form carbonaceous deposits on the catalyst so as to provide a carbon-containing catalyst; b) contacting at least a portion of the carbon-containing catalyst with a regeneration medium comprising oxygen in a regeneration zone comprising a fluid bed regenerator having a dense fluid phase and a dilute fluid phase under conditions effective to obtain a regenerated catalyst portion, wherein the difference between the temperature of the dilute phase and the temperature of the dense phase is no greater than 100 DEG C.; c) introducing said regenerated catalyst portion into said reaction zone; and d) repeating steps a)-c).

Description

The method of the temperature difference in the revivifier of attenuating oxygenate to olefin

The field of the invention

The present invention relates to be used to lower the method for the temperature difference in the revivifier of oxygenate to olefin.

Background of the present invention

Light olefin is defined as ethene at this paper, propylene, and butylene and their mixture are as the raw material of producing many important chemical and polymkeric substance.Generally, light olefin is produced by the cracking petroleum.Because the supply on restriction of competitive petroleum, be restricted by the chance of the low-cost light olefin of petroleum production.Increase in order to develop the effort of paying based on the light-olefin production technology of alternative materials.

The important alternative materials of one class of producing light olefin is an oxygenatedchemicals, alcohol for example, especially methyl alcohol and ethanol, dme, methyl ethyl ether, diethyl ether, methylcarbonate, and methyl-formiate.Many can production in these oxygenatedchemicalss by fermenting, or origin comes from the synthetic gas of Sweet natural gas, petroleum liquid, carbonaceous material comprises coal, recycled plastic, Municipal waste or any organic materials are produced.Because wide material sources, alcohol, alcohol derivate and other oxygenatedchemicals promise to be the non-petroleum sources of the economy of light-olefin production.

Be used to promote that oxygenate is that the catalyzer of alkene is a molecular sieve catalyst.Because ethene and propylene are the products that this reaction is wanted most, so that what catalyzer research concentrates on is the highest and increase catalyst life and increase on the optionally method of catalyzer to ethene and/or propylene to the selectivity of ethene and/or propylene.

Oxygenatedchemicals-conversion of olefines produces and has deposited carbonaceous material (coke) on the molecular sieve catalyst that is used for this conversion process of catalysis.Excessively accumulating of these carbon-containing sediments will influence the ability that catalyzer promotes reaction.For fear of the accumulation of undesirable coke on molecular sieve catalyst, oxygenatedchemicals-conversion of olefines method has been introduced second step that comprises catalyst regeneration.In regenerative process,, recovered the catalytic activity of catalyzer like this by removing coke from catalyzer with the oxygen burning.This regenerated catalyst can be used further to the catalysis oxygenatedchemicals then to conversion of olefines.

Generally, oxygenatedchemicals-conversion of olefines and regeneration are carried out in two autonomous container.The close-burning catalyzer is continuously discharged in the regeneration container from the reaction vessel that is used for transforming, and discharges regenerated catalyst and turning back to continuously from this regeneration container and be used in the reaction vessel transforming.

U.S. patent Nos.6,023,005 and 6,166,282 disclose the method for producing ethene and propylene by the catalyzed conversion of oxygenatedchemicals in utilizing the fluidized bed reaction method of catalyst regeneration, and the two introduces for reference here.

European patent application EP 1142639A discloses the activated source that will be dissolved in the hydrogenation component in the non-aqueous solvent and has joined the non-zeolite molecular sieve catalysed particulate that micro pore volume reduces seldom or do not have to reduce, so that hydrocracking to be provided, catalytic dewaxing and for the method for the isomerized improvement catalytic performance of the wax shape raw material that obtains to improve lubricating oil.This hydrogenation component can join in the catalyzer of two (beta-diketon root) metal (II) complex form.

U.S. patent No.4,350,614 (Schwartz) have instructed in fluid catalytic cracking (FCC) method and to have introduced the application that combines to the input of breeding blanket of platinum metals modified catalyst and increase oxygen, thereby the close phase of burning but not carbon monoxide in the dilute phase, thereby be reduced in two kinds of temperature difference between the phase, reduced the temperature of dilute phase significantly, the only appropriate simultaneously temperature that increases close phase.

U.S. patent No.4,072,600 (Schwartz) and U.S. patent No.4,151,121 people such as () Gladrow provide other of the purposes that relates in the CO oxidation of platinum metals in the FCC unit open.Be used in the presence of water, to use, and have high reactivity, make it possible to use alumina supporter at the catalyzer of the platinum group metal of the CO burning of FCC.

In the revivifier of methanol-to-olefins (MTO) method for transformation, under the situation that does not have CO ignition dope metal, carbon-containing sediment to the oxidation of CO than CO to CO ₂Conversion want fast.Because its speed is slower, so CO to CO ₂Conversion always not closely finish in mutually in the bottom of fluid bed regenerator.When this was reflected at top freeboard of fluidized bed generation, the result was that temperature raises, and is easy to above 100 ℃.This phenomenon usually is called as " burn the back ".Back burning in the dilute phase of the top of revivifier can cause excessive temperature, causes regenerator vessel or the breaking-up or the potentiality infringement of other assembly of containing at container.

Many metals are known can to promote that CO is oxidized to CO ₂Example is Pt or the Pd that uses in the catalytic converter of automobile.Yet the reaction of the known meeting catalysis of these identical metals and light olefin and hydrogen is as hydrogenation or hydrocracking reaction.These are reflected in the oxygenate to olefin is undesirable, because they will cause the reduction of the yield of these light olefins.

Thereby, usefully, provide by using the CO oxidized metal that carbon-containing sediment is converted into CO fully in mutually at the close of revivifier ₂And avoid or reduce back burning in the revivifier, significantly be not reduced in the method that optionally by oxygenatedchemicals prepare alkene to main alkene of oxygenatedchemicals to the olefin reactor.

General introduction of the present invention

The present invention is that the method that comprises the product of light olefin has solved the current demand in this area by the feedstock conversion that will comprise oxygenatedchemicals is provided.Method of the present invention is carried out in reactor assembly.As used herein term " reactor assembly " is meant and comprises the device of oxygenatedchemicals at least one place of olefin reaction wherein takes place.The term " reaction zone " that this paper uses in addition is meant the section of oxygenatedchemicals to olefin reaction takes place in reactor assembly, with term " reactor " synonym.Ideally, reactor assembly comprises reaction zone, entrance region and disengaging zone." entrance region " is the section of introducing raw material and catalyzer in reactor assembly." reaction zone " is that charging partly is converted into the section that contacts under the condition of light olefins product with catalyzer at effective oxygenatedchemicals with charging in reactor assembly." disengaging zone " is any other solid and the isolating section of product in catalyzer and the reactor in reactor assembly.Typically, reaction zone is between entrance region and disengaging zone.

The present invention relates to prepare the method for olefin product, comprising by oxygen-containing compound material:

A) allow raw material in reaction zone with comprise i) have the molecular sieve of regulation bore size and ii) the CO oxidized metal catalyzer effectively with feedstock conversion for comprising C ₂-C ₃The olefin product materials flow of alkene with contact under with the condition that carbon-contained catalyst is provided forming carbon-containing sediment on the catalyzer;

B) allow at least a portion and the regenerating medium that comprises oxygen of this carbon-contained catalyst comprise that having close fluid contacts mutually with in the breeding blanket of the fluid bed regenerator of rare fluid phase under the condition that effectively obtains regenerated catalyst portion, wherein the difference between the temperature of the temperature of dilute phase and close phase is not higher than 100 ℃;

C) described regenerated catalyst portion is incorporated into described reaction zone; With

D) repeating step a)-c).

In one embodiment, described temperature head is not higher than 50 ℃, is not higher than 20 ℃, or even is not higher than 10 ℃.

In another embodiment, regenerated catalyst portion has the carbon-containing sediment that is less than 5.0wt%, is less than the carbon-containing sediment of 3wt%, or even less than the carbon-containing sediment of 1wt%.

In another embodiment, carbon-contained catalyst has the carbon-containing sediment that is no less than 5wt%, is no less than the carbon-containing sediment of 3wt%, or even is not less than the carbon-containing sediment of 1wt%.

In a further embodiment, the CO oxidized metal comprises and is selected from VB family, group vib, the element in VIIB family and the VIII family metal.

In another embodiment, VB family metal is V (vanadium), and described group vib metal is selected from Cr, and Mo and W, described VIIB family metal are that Mn and described VIII family metal are selected from Ni, Ru, Rh, Pd, Os, Ir and Pt.

In another embodiment, the CO oxidized metal comprises Pt.

In another embodiment, add greater than the form of the opening diameter of molecular sieve with outside dimension the CO oxidized metal.

In a further embodiment, add with the form of methyl ethyl diketone platinum the CO oxidized metal.

In going back an embodiment, this molecular sieve catalyst has the aperture less than 5.0 , and for example molecular sieve catalyst comprises at least a framework of molecular sieve type that is selected from following group: AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG and THO.Other molecular sieve that is fit to comprises and is selected from ZSM-5, ZSM-4, erionite and chabazite, SAPO-34, SAPO-17, SAPO-18, those in MeAPSO and their the replacement group.

In one embodiment, molecular sieve catalyst has the aperture of 5-10 , and for example, molecular sieve catalyst comprises and is selected from MFI, MEL, MTW, EUO, MTT, HEU, FER, AFO, AEL, at least a framework of molecular sieve type in TON and their the replacement group.

In another embodiment of method of the present invention, to the selectivity of ethene and propylene with compare in the control methods that does not have to carry out in the presence of the described CO oxidized metal differ be no more than ± 5%.

In another embodiment of method of the present invention, compare with the same procedure of under the situation that does not have described CO oxidized metal, carrying out, the not reduction of selectivity % of ethene and propylene.

In another embodiment, the CO oxidized metal is to be no more than 5% amount based on total catalyst weight, 1% the amount that for example is no more than based on total catalyst weight exists, that is to say, to be no more than amount based on the 5000ppm of total catalyst weight, be no more than amount, or even surpass amount existence based on the 100ppm of total catalyst weight based on the 500ppm of total catalyst weight.

In another embodiment, the CO oxidized metal is platinum and exists with the amount based on the 0.1-10000ppm of total catalyst weight, and for example the CO oxidized metal is platinum and exists with the amount based on the 1-5000ppm of total catalyst weight.

In a further embodiment, the CO oxidized metal is a vanadium and with the amount of 5000-100000ppm catalyst weight, and for example the amount based on the 10000-50000ppm of total catalyst weight exists.

In an embodiment of method of the present invention, the CO oxidized metal separated joining in this method with described catalyzer.

In another embodiment, by the breeding blanket CO oxidized metal is joined in this method.

In another embodiment, the CO oxidized metal is joined in this method by reaction zone.

In a further embodiment, by ion-exchange the CO oxidized metal is joined in the catalyzer.

In another embodiment, keep 500-750 ℃ temperature at the close fluid of revivifier in mutually.

In going back an embodiment, the dispersion level of CO oxidized metal is " low to moderate ", is defined as the H of 0.1-0.7 for Pt: the Pt ratio.

The accompanying drawing summary

Fig. 1 shows and comprises high flow rate fluidized-bed with catalyst recycle and the reactor assembly that is used for the revivifier of oxygenate to olefin of the present invention.

Fig. 2 shows in the presence of the catalyzer that does not contain the CO oxidized metal, the time dependent temperature profile of measuring in oxygenatedchemicals to the revivifier head of olefine reaction apparatus and regenerator bed.

Fig. 3 shows in the presence of the catalyzer that contains the CO oxidized metal, the time dependent temperature profile of the reactor of measuring in oxygenatedchemicals to the revivifier head of olefine reaction apparatus and regenerator bed.

Detailed description of the present invention

Molecular sieve and catalyzer

Molecular sieve has various chemistry and physical, framework feature.Molecular sieve has been carried out abundant classification by the StructureCommission of the International Zeolite Association according to the principle of the IUPACCommission on Zeolite Nomenclature.Framework types has been described and has been constituted this skeleton, and the connection and the topological framework of the tetrahedral coordination atom of specified property are provided for these materials.Framework types zeolite and determined that the zeolite-type molecular sieve of structure is given three alphanumeric codes, and be described in the Atlas of Zeolite FrameworkTypes, the 5th edition, Elsevier, London, in the Britain (2001), they introduce for reference in this article comprehensively.

The limiting examples of these molecular sieves is small pore molecular sieves, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG, THO and their replacement form; Mesoporous molecular sieve, AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON and their replacement form; And large pore molecular sieve, EMT, FAU and their replacement form.Other molecular sieve comprises ANA, BEA, CFI, CLO, DON, GIS, LTL, MER, MOR, MWW and SOD.Preferred molecular sieve, the feedstock conversion that is particularly useful for containing oxygenatedchemicals are that the non-limitative example of the molecular sieve of alkene comprises AEL, AFY, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON.In a preferred embodiment, molecular sieve of the present invention has AEI topological framework or CHA topological framework, or their combination, most preferably the CHA topological framework.

Molecular screen material has common angle TO ₄Tetrahedral three-dimensional, the four sides connects skeleton structure, and wherein T is any tetrahedral coordination positively charged ion.The general size of the ring in hole according to the rules of these molecular sieves is described, and wherein this size is a benchmark with the T atomicity in the ring.Other framework types characteristic comprises the arrangement of the ring that forms cage type, when existing, and the size of passage and the space between cage type.Referring to people such as van Bekkum, Introduction to Zeolite Science andPractice, Second Completely Revised and Expanded Edition, the 137th volume, 1-67 page or leaf, Elsevier Science, B.V., Amsterdam, Holland (2001).

Little, in and large pore molecular sieve have 4 and encircle 12 ring or more ring framework types, in a preferred embodiment, zeolite molecular sieve has 8,10 or 12 ring structures or even more macrocyclic structure and mean pore size are that about 3  are to 15 .In the most preferred embodiment, molecular sieve of the present invention, preferred silicoaluminophosphamolecular molecular sieve have 8 rings and mean pore size less than about 5 , and preferred 3  are to about 5 , and more preferably 3  are to about 4.5 , and most preferably 3.5  arrive about 4.2 .

Molecular sieve, especially zeolite and zeolite-type molecular sieve preferably have one, preferred two or more angle [TO altogether ₄] tetrahedron element, more preferably two or more [SiO ₄], [AlO ₄], and/or [PO ₄] tetrahedron element, most preferably [SiO ₄], [AlO ₄], and/or [PO ₄] molecular skeleton of tetrahedron element.These silicon, aluminium and phosphorus type molecular sieve and metallic silicon, aluminium and phosphorus type molecular sieve have been described in detail in many publications, for example comprise U.S. patent No.4,567,029 (MeAPO, wherein Me is Mg, Mn, Zn or Co), U.S. patent No.4,440,871 (SAPO), and European patent application EP-A-0 159 624 (ELAPSO, wherein EI is As, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S. patent No.4,554,143 (FeAPO), U.S. patent No.4,822,478,4,683,217,4,744,885 (FeAPSO), EP-A-0 158 975 and U.S. patent No.4,935,216 (ZnAPSO), EP-A-0 161 489 (CoAPSO), EP-A-0 158 976 (ELAPO, wherein EL is Co, Fe, Mg, Mn, Ti or Zn), U.S. patent No.4,310,440 (AlPO ₄), EP-A-0 158 350 (SENAPSO), U.S. patent No.4,973,460 (LiAPSO), U.S. patent No.4,789,535 (LiAPO), U.S. patent No.4,992,250 (GeAPSO), U.S. patent No.4,888,167 (GeAPO), U.S. patent No.5,057,295 (BAPSO), U.S. patent No.4,738,837 (CrAPSO), U.S. patent No.4,759,919 and 4,851,106 (CrAPO), U.S. patent No.4,758,419,4,882,038,5,434,326 and 5,478,787 (MgAPSO), U.S. patent No.4,554,143 (FeAPO), U.S. patent No.4,894,213 (AsAPSO), U.S. patent No.4,913,888 (AsAPO), U.S. patent Nos.4,686,092,4,846,956 and 4,793,833 (MnAPSO), U.S. patent Nos.5,345,011 and 6,156,931 (MnAPO), U.S. patent No.4,737,353 (BeAPSO), U.S. patent No.4,940,570 (BeAPO), U.S. patent Nos.4,801,309,4,684,617 and 4,880,520 (TiAPSO), U.S. patent Nos.4,500,651,4,551,236 and 4,605,492 (TiAPO), U.S. patent No.4,824,554,4,744,970 (CoAPSO), U.S. patent No.4,735,806 (GaAPSO), (QAPSO, wherein Q is oxide compound skeleton unit [QO to EP-A-0 293937 ₂], and U.S. patent No.4,567,029,4,686,093,4,781,814,4,793,984,4,801,364,4,853,197,4,917,876,4,952,384,4,956,164,4,956,165,4,973,785,5,241, in 093,5,493,066 and 5,675,050, all these patents are introduced for reference at this paper comprehensively.

Other molecular sieve is included in EP-0 888 187B1 (microporous crystalline metal phosphate, SAPO ₄(UIO-6)), U S. patent No.6,004,898 (molecular sieve and alkaline-earth metal), the U.S. patent application serial number 09/511 that on February 24th, 2000 proposed, 943 (integrated hydrocarbon promotors), disclosed PCT WO 01/64340 on September 7 calendar year 2001 (thoriated molecular sieve), and R.Szostak, Handbook of Molecular Sieves, Van Nostrand Reinhold, those molecular sieves described in New York (1992), all these documents are introduced for reference at this paper comprehensively.

Most preferred siliceous, the molecular sieve of aluminium and/or phosphorus, and contain aluminium, phosphorus comprises aluminate or phosphate (ALPO) molecular sieve with the molecular sieve of the silicon of choosing wantonly, aluminosilicophosphate (SAPO) molecular sieve and replacement, ALPO and SAPO molecular sieve that preferable alloy replaces.Most preferred molecular sieve is the SAPO molecular sieve that SAPO molecular sieve and metal replace.In one embodiment, this metal is the IA family basic metal of the periodic table of elements, the alkaline-earth metal of the IIA family of the periodic table of elements, and the rare earth metal of IIIB family comprises lanthanide series metal: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; With the scandium or the yttrium of the periodic table of elements, the IVB of the periodic table of elements, VB, VIB, VIIB, the transition metal of VIIIB and IB family, or any mixture of these metallicses.In a preferred embodiment, this metal is selected from Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr, and their mixture.In another preferred embodiment, above-mentioned these atoms metals are by tetrahedron element, as [MeO ₂] be inserted in the skeleton of molecular sieve, and carry net charge according to the valency of metal substituent.For example, in one embodiment, when the metal substituent have+2 ,+3 ,+4 ,+5 or+during 6 valence state, the net charge of this tetrahedron element is-2 to+2.

In one embodiment, as representing by the mutatis mutandis following empirical formula of moisture-free basis at the molecular sieve described in above-mentioned many U.S. patents:

mR:(M _xAl _yP _z)O ₂，

Wherein R represents at least a template, preferred organic formwork agent; M is mole number/mole (M of R _xAl _yP _z) O ₂Has 0-1 with m, preferably 0-0.5 and the most preferably value of 0-0.3; X, y and z represent the Al as tetrahedral oxide, the molar fraction of P and M, wherein M is the IA that is selected from the periodic table of elements, IIA, IB, IIIB, IVB, VB, VIB, VIIB, the metal in one of VIIIB family and lanthanon.Preferably, M is selected from Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, a kind of among Zn and the Zr.In one embodiment, m is more than or equal to 0.2, and x, and y and z are more than or equal to 0.01.

In another embodiment, m is greater than 0.1 to about 1, and x is greater than 0 to about 0.25, and y is that 0.4-0.5 and z are 0.25-0.5, and more preferably m is 0.15-0.7, and x is 0.01-0.2, and y is that 0.4-0.5 and z are 0.3-0.5.

The non-limitative example of SAPO of the present invention and ALPO molecular sieve comprises SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. patent No.6,162,415), SAPO-47, SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, ALPO-46, and a kind of or mixture of their metallic molecular sieve.Preferred zeolite-type molecular sieve comprises SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, a kind of or mixture among ALPO-18 and the ALPO-34, more preferably SAPO-18 also, SAPO-34, ALPO-34 and ALPO-18, and a kind of or mixture in their the metallic molecular sieve, most preferably SAPO-34 and ALPO-18, and a kind of or mixture in their the metallic molecular sieve.

In one embodiment, molecular sieve is the coexisting material that has two or more different crystal structure phases in a kind of combination of molecular sieve.Especially, coexisting molecular sieve is described among the U.S. patent application serial number 09/924,016 that proposes August 7 calendar year 2001 and on April 16th, the 1998 disclosed PCT WO 98/15496, and the two introduces for reference here comprehensively.In another embodiment, molecular sieve comprises the coexisting phase of at least a AEI and CHA framework types.For example, SAPO-18, ALPO-18 and RUW-18 have the AEI framework types, and SAPO-34 has the CHA framework types.

Molecular sieve is synthetic

The synthetic of molecular sieve is described in above-mentioned many reference.Generally, molecular sieve is by one or more of aluminium source, phosphorus source, silicon source, and the hydrothermal crystallization method of template and metallic compound is synthesized.Generally, with silicon source, aluminium source and phosphorus source, optional mixture with one or more template and/or one or more metallic compounds is put in the optional sealed pressure vessel with inert plastic such as teflon lined, under crystallization pressure and temperature, heat, till forming crystalline material, by filtering, centrifugal and/or decantation reclaims then.

In a preferred embodiment, molecular sieve passes through to form the silicon source, the aluminium source, and the phosphorus source, organic formwork agent, the reaction product of preferred nitrogenous organic formwork agent and one or more polymkeric substance alkali is synthesized.This especially preferred embodiment has caused the synthetic of aluminosilicophosphate crystalline material, then by filter, centrifugal and/or decantation separates.

The limiting examples in silicon source comprises silicate, pyrogenic silica, for example available from Degussa Inc., the Aerosil-200 in New York, with CAB-O-SIL M-5, silicon compound such as orthosilicic acid tetraalkyl ester, for example original quanmethyl silicate (TMOS) and tetraethyl orthosilicate (TEOS), colloid silica or their aq suspension are for example available from E.I.du Pontde Nemours, Wilmington, the Ludox-HS-40 colloidal sol of Delaware, silicic acid, alkalimetal silicate, or their any mixture.The preferred source of silicon is a silicon sol.

The limiting examples in aluminium source comprises and contains al composition, as aluminium alcoholates, and aluminum isopropylate for example, aluminum phosphate, aluminium hydroxide, sodium aluminate, pseudobochmite, gibbsite and aluminum chloride, or their any mixture.Preferred aluminium source is a pseudobochmite, especially when producing silicoaluminophosphamolecular molecular sieve.

The limiting examples in phosphorus source (can also comprise aluminiferous phosphorus component) comprises phosphorated component (inorganic or organic), as phosphoric acid, and organophosphate such as triethyl phosphate, or crystallization or amorphous aluminate or phosphate such as AlPO ₄, trivalent microcosmic salt, or their mixture.Preferred phosphorus source is a phosphoric acid, especially when producing aluminosilicophosphate.

Template generally is the VA family element that contains the oxygen element periodictable, nitrogen especially, phosphorus, arsenic and antimony, more preferably nitrogen or phosphorus, most preferably nitrogen compound.The typical template agent of the VA family of the periodic table of elements also contains at least one alkyl or aryl, preferably has 1-10 carbon atom, more preferably the alkyl or aryl of 1-8 carbon atom.Preferred template is nitrogenous compound such as amine and quaternary ammonium compound.

In one embodiment, quaternary ammonium compound general formula R ₄N ⁺Represent that wherein each R is hydrogen or alkyl or substituted hydrocarbon radical, preferably have the alkyl or aryl of 1-10 carbon atom.In one embodiment, template comprises the mixture of one or more quaternary ammonium compounds and one or more monoamines, diamines or triamine.

The non-limitative example of template comprises tetraalkyl ammonium compound (salt that comprises them) as tetramethyl-ammonium compound (salt that comprises them), tetraethyl ammonium compound (salt that comprises them), tetrapropyl ammonium compound (salt that comprises them) and TBuA compound (salt that comprises them), cyclo-hexylamine, morpholine, di-n-propyl amine (DPA), tripropylamine, triethylamine (TEA), trolamine, piperidines, cyclo-hexylamine, the 2-picoline, N, N-dimethyl benzyl amine, N, N-diethylethanolamine, dicyclohexylamine, N, N-dimethylethanolamine, choline, N, N '-lupetazin, 1,4-diazabicyclo (2,2,2) octane, N ', N ', N, N-tetramethyl--(1,6) hexane diamines, N methyldiethanol amine, the N-Mono Methyl Ethanol Amine, N-methyl piperidine, 3-methyl-piperidines, N-methylcyclohexyl amine, 3-picoline, 4-picoline, rubane, N, N '-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; Di-n-butyl amine, neo-pentyl amine, two n-pentyl amine, isopropylamine, tert-butylamine, quadrol, tetramethyleneimine and 2-imidazolidone.

Preferred template or template are the tetraethyl ammonium compounds, and as tetraethyl ammonium hydroxide (TEAOH), the phosphoric acid tetraethyl ammonium is fluoridized tetraethyl ammonium, tetraethylammonium bromide, etamon chloride and acetate tetraethyl ammonium.Most preferred template is tetraethyl ammonium hydroxide and salt thereof, especially when producing silicoaluminophosphamolecular molecular sieve.In one embodiment, any two or more one or more and polymkeric substance alkali in mixture and silicon source, aluminium source and phosphorus source of above-mentioned template is used in combination.

Can be used for polymkeric substance alkali of the present invention, especially solubility or non-ionic polymers alkali are to have to be enough to the synthetic set molecular sieve of control, especially those of the required pH of SAPO molecular sieve.In a preferred embodiment, polymkeric substance alkali be solubility or this polymkeric substance alkali be nonionic alkali, preferred polymers alkali is nonionic and soluble polymer alkali, most preferably this polymkeric substance alkali is the polymkeric substance imines.In one embodiment, polymkeric substance alkali of the present invention has greater than 7 to about 14, more preferably about 8 to about 14, most preferably about aqueous solution of 9 to 14, the especially pH of water

In another embodiment, non-volatile polymkeric substance alkali general formula: (R-NH) _xRepresent that wherein (R-NH) is polymkeric substance or monomeric unit, wherein R contains 1-20 carbon atom, preferred 1-10 carbon atom, more preferably 1-6 carbon atom, most preferably 1-4 carbon atom; X is 1-500,000 integer.In one embodiment, R is linearity, branching or cyclic polymer, monomer, and chain preferably has the linear polymer chain of 1-20 carbon atom.

In another embodiment, polymkeric substance alkali is water miscibility polymkeric substance alkali, preferably in the aqueous solution.In another embodiment, polymkeric substance alkali is the polymine of representing with following general formula:

(NHCH ₂CH ₂-) _m[N (CH ₂CH ₂NH ₂) CH ₂CH ₂-] _n), wherein m is 10-20,000 and n be 0-2,000, preferred 1-2000.

In another embodiment, polymkeric substance alkali of the present invention has about 500 to about 1,000,000, preferably approximately 2,000 to about 800,000, more preferably about 10,000 to about 750,000, most preferably about 50,000 to about 750,000 molecular-weight average.

In another embodiment, contain the monomeric unit of polymkeric substance alkali of the present invention of a basic group and the mol ratio of template and be lower than 20, preferably be lower than 12,,, further preferably be lower than 5, most preferably be lower than 4 also more preferably less than 8 more preferably less than 10.

The limiting examples of polymkeric substance alkali comprises: Epicholorohydrin modified polyethyleneimine, ethoxylation polymine, polypropylene imines, the tree-shaped polymkeric substance of diamines (DAB-Am-n), poly-(allyl amine) [CH ₂CH (CH ₂NH ₂)] _n, poly-(1,2-dihydro-2,2,4-trimethylquinoline) and poly-(dimethyl amine-Epicholorohydrin-quadrol).

In another embodiment, the present invention relates to utilize template, preferred organic formwork agent, as organic amine, the method that ammonium salt and/or ammonium hydroxide and polymkeric substance alkali such as polymine come synthesis of molecular sieve.

In the typical case of molecular sieve is synthetic, be mixed together at neutralize one or more template and polymkeric substance alkali of solvent such as water with basic metal the component of phosphorous, aluminium and/or silicon is optional, preferably stir simultaneously and/or inoculate with crystalline material, to form synthetic mixture, then as in U.S. patent Nos.4,440,871,4,861,743,5,096,684 and 5, the crystallization condition of the pressure and temperature described in 126,308 is heating down, and all these patents are introduced for reference at this paper comprehensively.Polymkeric substance alkali and at least a template, with one or more aluminium sources, phosphorus source and silicon source merge with any order, for example mix simultaneously with one or more sources, with one or more sources and/or template premix, after merging etc. with described source and template.

Generally, above-mentioned synthetic mixture is sealed in container and heat (preferably under autogenous pressure) to about 80 ℃ to about 250 ℃, 100 ℃ to about 250 ℃ of preferably approximatelies, more preferably about 125 ℃ to about 225 ℃, also more preferably about 150 ℃ are arrived about 180 ℃ temperature.In another embodiment, the hydrothermal crystallization temperature is lower than 225 ℃, preferably is lower than 200 ℃ to about 80 ℃, more preferably less than 195 ℃ to about 100 ℃.

In another embodiment, Tc raises in building-up process gradually or progressively, and preferred Tc keeps the constant time that reaches effective formation crystalline product.Form the required time of crystalline product and generally be immediately to several weeks, the time length is depended on temperature usually; Temperature is high more, and the time length is short more.In one embodiment, crystalline product arrived about 2 weeks with about 30 minutes under heating, and preferably approximately 45 minutes to about 240 hours formed by about 120 hours in more preferably about 1 hour.

In one embodiment, the synthetic of molecular sieve helped by the seed from other or same structure types of molecules sieve.

Hydrothermal crystallization for example carries out under the situation of stirring or rotary drum processing being with or without stirring or mixing.Stirring during crystallization or mixing can be continuously or be interrupted, preferred continuously stirring.Typically, formed crystal molecule sieve product with slurry state usually, again by any standard technique known in the art, for example centrifugal or filtration is reclaimed.Isolating crystalline product washs one or many in one embodiment, typically uses liquid such as water.The crystalline product of washing is optional then to carry out drying, preferably in air.

A kind of method of crystalline comprises provides the aqueous reaction mixture that contains excessive template and polymkeric substance alkali, allow the crystallization under hydrothermal condition of this mixture, set up the balance between molecular sieve formation and the dissolving, remove some excessive template and/or organic basess then, to suppress the dissolving of molecular sieve.For example referring to U.S. patent No.5,296,208, this patent is introduced for reference at this paper comprehensively.

Crystalline another kind method relates in crystallisation process not stirred reaction mixture, and the reaction mixture that for example contains silicon, aluminium and/or phosphorus component and template and polymkeric substance alkali at least reaches for some time.Referring to disclosed PCT WO 01/47810 on June 5 calendar year 2001, this patent is introduced for reference at this paper comprehensively.

Other method of synthesis of molecular sieve or modified molecular screen is described in U.S. patent No.5,879,655 (ratios of control template agent and phosphorus), U.S. patent No.6,005, not 155 (use does not have the properties-correcting agent of salt), U.S. patent No.5,475,182 (acid extractions), U.S. patent No.5,962,762 (handling) with transition metal, U.S. patent Nos.5,925,586 and 6,153,552 (phosphorus modifications), U.S. patent No.5,925,800 (integral body supports), U.S. patent No.5,932,512 (fluorine processing), U.S. patent No.6,046,373 (hertzian wave is handled or modification), U.S. patent No.6,051,746 (polynuclear aromatic properties-correcting agent), U.S. patent No.6,225,254 (heated die plates), disclosed PCT WO 01/36329 on May 25 calendar year 2001 (tensio-active agent is synthetic), calendar year 2001 disclosed PCT WO 01/25151 on April 12 (segmented acid-adding), calendar year 2001 disclosed PCT WO 01/60746 on August 23 (silicone oil), the U.S. patent application serial number 09/929 that propose August 15 calendar year 2001,949 (cooling molecular sieves), the U.S. patent application serial number 09/615,526 (metal impregnation that comprises copper) that on July 13rd, 2000 proposed, the U.S. patent application No.09/672 that on September 28th, 2000 proposed, 469 (electroconductibility microfilters), and the U.S. patent application serial number 09/754,812 (lyophilize molecular sieve) of proposition on January 4 calendar year 2001, all these documents are introduced for reference at this paper comprehensively.

In a preferred embodiment, when using template in molecular sieve synthetic, preferably, by many known technologies, for example thermal treatment is as calcining basically, preferably removal fully crystallization after for this template.Calcining comprises allows molecular sieve and the gas that contains template, and the gas that preferably contains any oxygen that needs concentration contacts under the high temperature that is enough to partially or completely to decompose with this template of oxidation.

Molecular sieve have high silicon (Si) and aluminium (Al) than or low silicon and aluminum ratio, yet it is preferred that low Si/Al is compared to that SAPO synthesizes.In one embodiment, molecular sieve has and is lower than 0.65, preferably is lower than 0.40, more preferably less than 0.32 with most preferably be lower than 0.20 Si/Ar ratio.In another embodiment, molecular sieve has about 0.65 to about 0.10, the Si/Al ratio of preferably approximately 0.40 to about 0.10, more preferably about 0.32 to about 0.10, most preferably about 0.32 to about 0.15.

At least contain silicon, aluminium and/or phosphorus component, the pH of the reaction mixture of template and polymkeric substance alkali should be 2-10, preferred 4-9, most preferably 5-8.PH can be the preferable range of 4-9 with the pH that keeps in the building-up process by adding alkalescence as required or acidic cpd is controlled.In another embodiment, template and/or polymkeric substance alkali are joined in the reaction mixture in silicon source and phosphorus source, make the pH of reaction mixture be no more than 10.

In one embodiment, other molecular sieve of molecular sieve of the present invention and one or more combines.In another embodiment, preferred aluminosilicophosphate or aluminophosphate molecular sieve or their mixture be used in combination at one or more of the limiting examples of the molecular sieve of the following stated: β zeolite (U.S. patent No.3,308,069), ZSM-5 (U.S. patent Nos.3,702,886,4,797,267 and 5,783,321), ZSM-11 (U.S. patent No.3,709,979), ZSM-12 (U.S. patent No.3,832,449), ZSM-12 and ZSM-38 (U.S. patent No.3,948,758), ZSM-22 (U.S. patent No.5,336,478), ZSM-23 (U.S. patent No.4,076,842), ZSM-34 (U.S. patent No.4,086,186), ZSM-35 (U.S. patent No.4,016,245), ZSM-48 (U.S. patent No.4,397,827), ZSM-58 (U.S. patent No.4,698,217), MCM-1 (U.S. patent No.4,639,358), MCM-2 (U.S. patent No.4,673,559), MCM-3 (U.S. patent No.4,632,811), MCM-4 (U.S. patent No.4,664,897), MCM-5 (U.S. patent No.4,639,357), MCM-9 (U.S. patent No.4,880,611), MCM-10 (U.S. patent No.4,623,527), MCM-14 (U.S. patent No.4,619,818), MCM-22 (U.S. patent No.4,954,325), MCM-41 (U.S. patent No.5,098,684), M-41S (U.S. patent No.5,102,643), MCM-48 (U.S. patent No.5,198,203), MCM-49 (U.S. patent No.5,236,575), MCM-56 (U.S. patent No.5,362,697), ALPO-11 (U.S. patent No.4,310,440), titanoaluminosilicatmolecular (TASO), TASO-45 (EP-A-0 229 295), borosilicate (U.S. patent No.4,254,297), titanium aluminate or phosphate (TAPO) (U.S. patent No.4,500,651), the mixture of ZSM-5 and ZSM-11 (U.S. patent No.4,229,424), ECR-18 (U.S. patent No.5,278,345), the binding substances of SAPO-34 and ALPO-5 (U.S. patent No.5,972,203), disclosed PCT WO 98/57743 on December 23rd, 1998 (molecular sieve and fischer-tropsch catalysts), U.S. patent No.6,300,535 (in conjunction with the zeolites of MFI), and mesoporous molecular sieve (U.S. patent Nos.6,284,696,5,098,684,5,102,643 and 5,108,725), all these documents are introduced for reference at this paper comprehensively.

The method for preparing molecular sieve catalyst composition

In case synthesis of molecular sieve depends on the needs of specific method for transformation then this molecular sieve to be mixed with molecular sieve catalyst composition, is particularly useful for industrial application.By synthesis of molecular sieve and binding agent and/or substrate material are merged, form the molecular sieve catalyst composition of molecular sieve catalyst composition or preparation, thereby catalyzer is made or be mixed with to above synthetic molecular sieve.With known technology such as spraying drying, granulation, extrude etc. and will prepare molecular sieve catalyst composition and be formed with particle with shape and size.

There are many different binding agents to can be used for forming molecular sieve catalyst composition.Can be separately or the limiting examples of the binding agent that is used in combination comprise various types of hydrated aluminum oxides, silicon-dioxide and/or other inorganic oxide sol.A kind of preferred salic colloidal sol is Wickenol CPS 325 (aluminum chlorhydrol).Inorganic oxide sol works as glue, synthesis of molecular sieve and other material such as matrix is bonded together, especially after thermal treatment.When heating, inorganic oxide sol (preferably having low viscosity) is converted into the inorganic oxide matrix component.For example, alumina sol is converted into alumina host after thermal treatment.

Wickenol CPS 325, the hydroxylation aluminium type colloidal sol that contains the chlorine counter ion has Al _mO _n(OH) _oCl _pX (H ₂O) general formula, wherein m is 1-20, and n is 1-8, and o is 5-40, and p is that 2-15 and x are 0-30.In one embodiment, binding agent is Al ₁₃O ₄(OH) ₂₄Cl ₇12 (H ₂O), as people such as G.M.Wolterman, Stud.Surf.Sci.and Catal., 76, described in the 105-144 page or leaf (1993), the document is introduced for reference at this paper.In another embodiment, the example such as the aluminum oxyhydroxide of one or more binding agents and one or more other non-limiting alumina material, gama-alumina, boehmite, diaspore and conventional aluminium oxide such as Alpha-alumina, beta-alumina, gama-alumina, δ-aluminum oxide, ε-aluminum oxide, κ-aluminum oxide, ρ-aluminum oxide, aluminium hydroxide, as gibbsite, bayerite, nordstrandite, doyelite and their mixture are used in combination.

In another embodiment, binding agent is an alumina sol, mainly comprises aluminum oxide, optional some silicon that comprise.In another embodiment, binding agent is sour by using, and the peptization aluminum oxide that preferred not halogen-containing acid treatment hydrated alumina such as pseudobochmite are made is with preparation colloidal sol or aluminum ion solution.The limiting examples that is purchased colloidal alumina colloidal sol comprises can be from Nalco Chemical Co., Naperville, the Nalco 8676 that Illinois obtains and can be from ThePQ Corporation, Valley Forge, the Nyacol that Pennsylvania obtains.

In a preferred embodiment, above synthetic molecular sieve and one or more substrate materials are merged.Substrate material generally can effectively reduce the total catalyst cost; as the hot cave that helps the influence that for example the guard catalyst composition is not heated in regenerative process; make catalyst composition closely knit, increase catalyst strength such as crushing strength and resistance to abrasion, and in ad hoc approach, control conversion rate.

The limiting examples of substrate material comprises following one or more: rare earth metal, and metal oxide comprises titanium dioxide, zirconium white, magnesium oxide, Thorotrast, beryllium oxide, quartz, silicon-dioxide or colloidal sol, and their mixture, silica-magnesia for example, silicon-dioxide-zirconium white, silica-titania, silica-alumina and silica-alumina-Thorotrast.In one embodiment, substrate material is a natural clay as from those of montmorillonite and kaolin families.These natural claies comprise sabbentonites and for example are called as Dixie, McNamee, those kaolin of Georgia and Florida clay.The limiting examples of other substrate material comprises: halloysite (haloysite), kaolinite, dickite, nakrite, or anauxite.In one embodiment, to substrate material, preferred any clay carries out known method of modifying such as calcining and/or acid treatment and/or chemical treatment.

In a preferred embodiment, substrate material is clay or clay based composition, preferably has the clay or the clay based composition of low iron or content of titanium dioxide, and most preferably substrate material is a kaolin.Find that kaolin has formed pumpable highly filled slurry, it is long-pending that it has low fresh surface, and compress together easily owing to its platelets structure.Substrate material, most preferably kaolinic preferred average particle size are about 0.1 to about 0.6 μ m, and the D90 size-grade distribution is less than about 1 μ m.

In one embodiment, binding agent, molecular sieve and substrate material merge in the presence of liquid, form molecular sieve catalyst composition, wherein the amount of binding agent is about 2 to about 30wt%, preferably approximately 5 to about 20wt%, more preferably about 7 to about 15wt%, based on binding agent, the gross weight of molecular sieve and substrate material does not comprise liquid (after calcining).

In another embodiment, the binding agent that uses in forming molecular sieve catalyst composition and the weight ratio of substrate material are 0: 1 to 1: 15, preferred 1: 15 to 1: 5, and more preferably 1: 10 to 1: 4, most preferably 1: 6 to 1: 5.Have been found that higher molecular sieve content, lower matrix content has improved the molecular sieve catalyst composition performance, yet, lower molecular sieve content, higher matrix content has been improved the wear resistance of composition.

In liquid, merging when forming slurry with binding agent molecular sieve and substrate material are optional, need to mix, preferred strict mixing produces the basic uniform mixture that contains molecular sieve.The limiting examples that is fit to liquid comprises water, alcohol, ketone, aldehydes, and/or a kind of or mixture of ester class.Most preferred liquid is water.In one embodiment, this slurry being carried out colloidal grinding reaches and is enough to obtain required slurry quality (slurry texture), the time of inferior granularity and/or inferior size-grade distribution.

Molecular sieve and substrate material and optional binding agent are in identical or different liquid, with any order, together, simultaneously, according to the order of sequence or the combination of these modes merge.In preferred embodiments, use identical liquid, preferably water.Molecular sieve, substrate material and optional binding agent be as solid, substantially dry form or dried forms, or in liquid, merge together or independently as slurry.If solid adds together as the solid of drying or substantially dry, preferably add the liquid of limited and/or manipulated variable.

In one embodiment, the slurry with molecular sieve, binding agent and substrate material mixes or grinding the full and uniform slurry of the subparticle of acquisition molecular sieve catalyst composition, the shaped device of adding production molecular sieve catalyst composition then.In a preferred embodiment, shaped device is a spray-dryer.Typically, shaped device remains on is enough to remove under the temperature of most of liquid from slurry and gained molecular sieve catalyst composition.When forming by this way, the gained catalyst composition presents microspheroidal.

When using spray-dryer as shaped device, generally, common to add average inlet temperature be that 200-550 ℃ and general export temperature are 100 to about 225 ℃ spray-drying chamber with dry gas with the slurry of molecular sieve and substrate material and optional binding agent.In one embodiment, the mean diameter of the catalyst composition that spraying drying forms is about 40 to about 300 μ m, preferably approximately 50 to about 250 μ m, more preferably about 50 to about 200 μ m and most preferably about 65 to about 90 μ m.

In spray-drying process, allow slurry by slurry being assigned as the nozzle of small droplets, aerosol spray is collected kiln.Atomizing realizes to single-nozzle or a plurality of nozzle of the pressure drop of 1000psia (690kPaa is to 6895kPaa) by having 100psia by forcing this slurry.In another embodiment, this slurry and atomizing fluids such as air, steam, stack gas or any other suitable gas add single nozzle or a plurality of nozzle together jointly.

In another embodiment, above-mentioned slurry enters the periphery that slurry is assigned as the swiveling wheel of small droplets, and drop size is controlled by many factors, comprise slurry viscosity, the surface tension of slurry, flow velocity, pressure and temperature, its shape of nozzle and size, or the speed of rotation of wheel.These drops are dry in concurrent that passes through spray-dryer or counter-flow air then, to form substantially dry or exsiccant molecular sieve catalyst composition, more particularly, the molecular sieve of powder form.

Generally, control the granularity of powder to a certain extent by the solids content of slurry.Yet the granularity of catalyst composition and the control of spherical characteristic thereof can be controlled by changing slurry feeding performance and atomization condition.

Described other method (using the spraying drying of egr molecule sieve catalyst composition) that forms molecular sieve catalyst composition in the U.S. patent application serial number 09/617,714 that proposed on July 17th, 2000, this patent application is introduced for reference at this paper.

In another embodiment, the molecular sieve catalyst composition of preparation contains about 1 to about 99wt%, and more preferably about 5 to about 90wt%, most preferably about 10 to about 80wt% molecular sieve is based on the gross weight of molecular sieve catalyst composition.

In another embodiment, gross weight by binding agent, molecular sieve and substrate material, among the spray-dired molecular sieve catalyst composition or on the weight percent of binding agent be about 2 to about 30wt%, preferably approximately 5 to about 20wt%, more preferably about 7 to about 15wt%.

In case molecular sieve catalyst composition forms with basic state of doing or drying regime, in order further to harden and/or to activate formed catalyst composition, at high temperature heat-treat usually, as calcining.Common calcination environment is the air that generally comprises a small amount of water vapor.Typical calcining temperature is about 400 to about 1,000 ℃, and preferably approximately 500 is to about 800 ℃, and most preferably about 550 arrive about 700 ℃, preferably in calcination environment, as air, nitrogen, helium, stack gas (products of combustion of oxygen poorness), or in their any mixture.

In one embodiment, the calcining of the molecular sieve catalyst composition of being prepared is carried out in many known equipment, comprises the rotary calcining stove, fluidized bed calcination stove, batch furnace etc.The hardenability and the temperature that depend on molecular sieve catalyst, calcination time about typically 15 minutes to about 2 hours.

In a preferred embodiment, molecular sieve catalyst composition heats in nitrogen under about 700 ℃ temperature about 600.Heating was carried out general 30 minutes to 15 hours, and preferred 1 hour to about 10 hours, more preferably about 1 hour to about 5 hours, most preferably about 2 hours to about 4 hours time.

Being used for the activated molecular sieve catalyst composition (is the silicon source at molecular sieve especially, phosphorus source and aluminium source, under the situation of the reaction product of the mixture of template and polymkeric substance alkali), more specifically other method of silicon aluminium phosphate catalyst composition (SAPO) for example is described in U.S. patent No.5,185,310 (molecular sieve and the water of gel alumina are heated to 450 ℃), disclosed PCT WO 00/75072 on December 14th, 2000 (be heated to and stay an amount of template), with the U.S. application serial 09/558 that proposed on April 26th, 2000, in 774 (regeneration of molecular sieve), all these documents are introduced for reference at this paper.

The limiting examples of substrate material comprises following one or more: rare earth metal, and metal oxide comprises titanium dioxide, zirconium white, magnesium oxide, Thorotrast, beryllium oxide, quartz, silicon-dioxide or colloidal sol, and their mixture, silica-magnesia for example, silicon-dioxide-zirconium white, silica-titania, silica-alumina and silica-alumina-Thorotrast.In one embodiment, substrate material is a natural clay as from those of montmorillonite and kaolin families.These natural claies comprise sabbentonites and for example are called as Dixie, McNamee, those kaolin of Georgia and Florida clay.The limiting examples of other substrate material comprises: halloysite, kaolinite, dickite, nakrite, or anauxite.In one embodiment, to substrate material, preferred any clay carries out known method of modifying such as calcining and/or acid treatment and/or chemical treatment.

In liquid, merging when forming slurry with binding agent molecular sieve and substrate material are optional, need to mix, preferred strict mixing produces the basic uniform mixture that contains molecular sieve.The limiting examples that is fit to liquid comprises water, alcohol, ketone, aldehydes, and/or a kind of or mixture of ester class.Most preferred liquid is water.In one embodiment, this slurry being carried out colloidal grinding reaches and is enough to obtain required slurry quality, the time of inferior granularity and/or inferior size-grade distribution.

In spray-drying process, allow slurry by slurry is assigned as small droplets nozzle, aerosol spray is collected kiln.Atomizing realizes to single-nozzle or a plurality of nozzle of the pressure drop of 1000psia (690kPaa is to 6895kPaa) by having 100psia by forcing this slurry.In another embodiment, this slurry and atomizing fluids such as air, steam, stack gas or any other suitable gas add single nozzle or a plurality of nozzle together jointly.

Described other method (using the spraying drying of egr molecule sieve catalyst composition) that forms molecular sieve catalyst composition in the U.S. patent application serial number 09/617,714 that proposed on June 17th, 2000, this patent application is introduced for reference at this paper.

In another embodiment, the molecular sieve catalyst composition of being prepared contains about 1 to about 99wt%, and more preferably about 5 to about 90wt%, most preferably about 10 to about 80wt% molecular sieve is based on the gross weight of molecular sieve catalyst composition.

Oxygenate to olefin

In a preferred embodiment of method of the present invention, raw material contains one or more oxygenatedchemicalss, and more particularly, one or more contain the organic compound of at least one Sauerstoffatom.In the most preferred embodiment of method of the present invention, the oxygenatedchemicals in raw material is one or more alcohol, and the preferred wherein aliphatic structure of alcohol partly has 1-20 carbon atom, preferred 1-10 carbon atom, the most preferably fatty alcohol of 1-4 carbon atom.Alcohol as raw material comprises lower straight and branched aliphatic alcohol class and their unsaturated counterpart in the method for the invention.

The limiting examples of oxygenatedchemicals comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, methyl ethyl ether, dme, diethyl ether, Di Iso Propyl Ether, formaldehyde, methylcarbonate, dimethyl ketone, acetate and their mixture.

In the most preferred embodiment, raw material is selected from methyl alcohol, ethanol, dme, one or more in diethyl ether or their mixture, more preferably methyl alcohol and dme, most preferably methyl alcohol.

Above-mentioned various raw material especially contains the raw material of oxygenatedchemicals, and the raw material that more specifically contains alcohol mainly is converted into one or more alkene.Alkene or olefinic monomer by this raw material production typically have 2-30 carbon atom, preferred 2-8 carbon atom, more preferably 2-6 carbon atom, also more preferably 2-4 carbon atom, most preferably ethene and/or propylene.

The limiting examples of olefinic monomer comprises ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene, optimal ethylene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene and their isomer.Other olefinic monomer comprises unsaturated monomer, has the diolefine of 4-18 carbon atom, conjugation or non-conjugated diene, polyenoid, vinyl monomer and cycloolefin.

In the most preferred embodiment, raw material, preferably the raw material of one or more oxygenatedchemicalss is converted in the presence of molecular sieve catalyst composition and has 2-6 carbon atom, the alkene of preferred 2-4 carbon atom.Most preferably, separately or as the alkene of mixture by containing oxygenatedchemicals, preferred alcohols, most preferably the feedstock conversion of methyl alcohol is preferred alkene ethene and/or propylene.

Having many methods to be used for feedstock conversion is alkene, comprises various cracking methods such as steam cracking, heat regeneration cracking, fluidized-bed cracking, fluid catalystic cracking, deep catalytic cracking and viscosity breaking.

Most preferred method is commonly referred to as methyl alcohol to conversion of olefines method (MTO).In the MTO method, usually, the oxidation raw material, the raw material that most preferably contains methyl alcohol is converted into one or more alkene in the presence of molecular sieve catalyst composition, preferably and mainly be ethene and/or propylene, usually is called as light olefin.

Being used to transform raw material, preferably containing in the embodiment of method of raw material of one or more oxygenatedchemicalss, is benchmark in the gross weight of the hydrocarbon produced, the output of alkene surpasses 50wt%, preferably surpass 60wt%, more preferably surpass 70wt%, most preferably surpass 75wt%.

Use molecular sieve catalyst composition to increase the optionally method of preferred hydrocarbon product such as ethene and/or propylene and be described in U.S. patent No.6 by being converted of oxygenatedchemicals, 137,022 (linear velocity), and the PCT WO 00/74848 (at least 0.13 methanol uptake index) of publication on December 14th, 2000, all these patents are introduced for reference at this paper comprehensively.

In one embodiment, raw material contains one or more thinners, typically is used for reducing the concentration of raw material, and does not generally react with raw material or molecular sieve catalyst composition.The limiting examples of thinner comprises helium, argon gas, nitrogen, carbon monoxide, carbonic acid gas, water, non-reacted substantially paraffinic (especially paraffinic hydrocarbons such as methane, ethane, and propane), non-reacted substantially aromatic substance and their mixture.Most preferred thinner is water and nitrogen, and wherein water is particularly preferred.

Diluent water is with liquid or vapor form, or uses with their mixture.Thinner or directly join in the raw material that enters reactor, or directly join in the reactor, or add with molecular sieve catalyst composition.In one embodiment, the amount of the thinner in the raw material is about 1 to about 99mol%, preferably approximately 1 to about 80mol%, and more preferably about 5 to about 50mol%, most preferably about 5 to about 25mol%, based on the total mole number of raw material and thinner.In one embodiment, other hydro carbons is directly or indirectly joined in the raw material, they comprise alkene, paraffinic hydrocarbons, aromatic substance is (for example referring to U.S. patent No.4,677,242, the interpolation of aromatic substance) or their mixture, preferred propylene, butylene, amylene, with have 〉=other hydro carbons of 4 carbon atoms or their mixture.

Be used in the presence of molecular sieve catalyst composition of the present invention, transforming raw material, especially the method that contains the raw material of one or more oxygenatedchemicalss is used in the interior reaction method of reactor and carries out, wherein this method is a fixed-bed approach, bed process, preferred continuous fluid bed process, most preferably continuous high speed bed process.

This reaction method can be at various catalyticreactors as having the dense bed that is coupled at together or the mixing reactor of fixed bed district and/or fast fluidized bed reaction zone, and circulating fluid bed reactor carries out in the riser reactor etc.The common response device type that is fit to for example is described in U.S. patent No.4,076,796, U.S. patent No.6,287,522 (double lifting leg) and FluidizationEngineering, D.Kunii and O.Levenspiel, Robert E.Krieger PublishingCompany, New York, in 1977, all these documents are introduced for reference at this paper comprehensively.

Preferred type of reactor is briefly to be described in Riser Reactor, Fluidizationand Fluid-Particle Systems, the 48-59 page or leaf, F.A.Zenz and D.F.Othmo, Reinhold Publishing Corporation, New York, 1960, U.S. patent No.6,166,282 (fast fluidized bed reactors), and the U.S. patent application serial number 09/564 that proposed on May 4th, 2000, riser reactor in 613 (multiple riser reactors), all these documents are introduced for reference at this paper comprehensively.

In a preferred embodiment, bed process or high flow rate bed process comprise reactor assembly, regeneration system rapidly and recovery system.

Reactor assembly is fluidized bed reactor system preferably, has first reaction zone and second reaction zone at least one separation vessel (preferably including one or more cyclone separators) in one or more riser reactors.In one embodiment, these one or more riser reactors and separation vessel contain at the single reaction container.With fresh feed, the raw material that preferably contains one or more oxygenatedchemicalss and optional one or more thinners adds these one or more riser reactors of wherein having introduced zeolite or zeolite-type molecular sieve catalyst composition or its coking modification.In one embodiment, molecular sieve catalyst composition or its coking modification and liquid or gas or their mixture contact, and are incorporated into afterwards in the riser reactor, and preferably this liquid is water or methyl alcohol, and this gas is rare gas element such as nitrogen.

In one embodiment, separately or with amount that steam feed is united the fresh feed that adds reactor assembly is 0.1 to arrive about 85wt%, preferably approximately 1 to about 75wt%, more preferably about 5 to about 65wt%, based on the gross weight of the raw material that comprises any thinner that wherein contains.Liquid and steam feed preferably have same composition, or contain the identical or different raw material of different ratios and identical or different thinner.

To the light olefin conversion process, carbon-containing sediment accumulates on the catalyzer of conversion reaction being used to promote at oxygenatedchemicals.From some viewpoint, gathering of these carbon-containing sediments caused that catalyzer is converted into oxygen-containing compound material the reduction of the ability of light olefin.In this, this catalyzer is by the part passivation.When catalyzer can not be olefin product with oxygenate again, this catalyzer was considered to complete passivation.As a step in the method for the invention, from reactor assembly, discharge a part of catalyzer, at least a portion of this part catalyzer of discharging from reactor is partial regeneration (if incomplete words) in revivifier.So-called regeneration is meant from catalyzer to small part removes carbon-containing sediment.That part of catalyzer of discharging from reactor ideally, is to the small part passivation.The catalyzer of the remainder in reactor assembly is not having recirculation under the regenerated situation.To cool off or not have the refrigerative regenerated catalyst to turn back in the reactor then.Ideally, to be used for the regenerated ratio be about 0.1 to about 99% of the catalyst ratio of discharging from reactor to the discharge section catalyzer.Better is, this ratio is about 0.2 to about 50%, most desirably, is about 0.5 to about 5%.

Ideally, catalyst regeneration carries out in the presence of the oxygen containing gas of bag.Air and with nitrogen or CO ₂The air of dilution is the ideal regeneration gas.Aerial oxygen concn can be reduced to the overheated controlled levels of reducing to minimum level or the generation of the hot spot in the revivifier being reduced to minimum level with revivifier.This catalyzer can also be used hydrogen, the mixture of hydrogen and carbon monoxide, or the also regeneration originally of other reducing gas that is fit to.

This catalyzer can be in many ways-intermittently, and continuously, combinations semicontinuous or these modes are regenerated.Continuous catalyst regeneration is the ideal method.It is desirable to, this catalyst regeneration arrives the level of the residual coke of about 15wt% to about 0.01 of this catalyst weight.

Catalyst regeneration temperature should be about 250 to about 750 ℃, about ideally 500 to about 700 ℃.Can use interchanger that the temperature in the revivifier is controlled to required scope.

When the regenerated catalyst from revivifier turned back to reactor assembly, it can turn back to the disengaging zone, reaction zone, and/or entrance region.It can also turn back to the conduit that catalyzer is recycled to entrance region from the disengaging zone.

Ideally, catalyst regeneration is with at first remove carrying out to the small part catalyst deactivation of organic materialss (organism) that great majority remove easily in stripper or stripping zone.This stripping can be by at high temperature allowing stripping gas realize by spent catalyst.Be suitable for steam stripped gas and comprise steam, nitrogen, helium, argon gas, methane, CO ₂, CO, hydrogen and their mixture.Preferred gas is steam.The gas hourly space velocity of stripping gas (GHSV is by the volumeter of gas volume/catalyzer and coke) is about 0.1 to about 20,000h ^-1Acceptable stripping temperature is about 250 to about 750 ℃, about ideally 350 to about 675 ℃.

Therefore the raw material that enters reactor assembly preferably partially or completely is converted into the gaseous effluent that enters separation vessel with coked molecular sieve catalyst composition in first reaction zone.In preferred embodiments, the cyclone separator in separation vessel is designed in the disengaging zone isolated molecule sieve catalyst composition from the gaseous effluent that contains one or more alkene, preferred coked molecular sieve catalyst composition.Cyclone separator is preferred, however also separating catalyst composition from gaseous effluent of the gravitational effect in separation vessel.Be used for comprising use plate, cover, bend pipe etc. from other method of gaseous effluent separating catalyst composition.

In an embodiment of separation system, separation system comprises separation vessel, and typically, the bottom of separation vessel is a stripping zone under these conditions.

Being used for oxygenate is that the temperature of light olefin depends in part on catalyzer at least, the configuration of the share of the regenerated catalyst in the catalyst mixture and reactor assembly and reactor and changing in wide region.At method for transformation, the invert point of more specifically using in reactor assembly is about 200 ℃ to about 1000 ℃, 250 ℃ to about 800 ℃ of preferably approximatelies, more preferably about 250 ℃ to about 750 ℃, also more preferably about 300 ℃ to about 650 ℃, further preferably approximately is 350 ℃ to about 600 ℃, most preferably about 350 ℃ to about 550 ℃.Lower temperature has generally caused lower speed of response, and the formation speed of required light olefins product can be significantly slack-off.Yet, being higher than under 700 ℃ the temperature, this method may not form the light olefins product of optimum quantity, and the speed that coke on catalyzer and light saturates form can become too high.

Form (although may not with optimum quantity) under the pressure of light olefin in wide region, include, but are not limited to autogenous pressure and approximately 0.1kPa to the pressure of about 100MPa.Ideal pressure is that about 6.9kPa arrives about 34MPa, and most desirably approximately 20kPa arrives about 500kPa.Aforementioned pressure does not comprise if the pressure of the thinner that has, and is meant the dividing potential drop of charging, when it relates to oxygenatedchemicals and/or their mixture.Can use the pressure outside described scope, and be within the scope of the invention.Extremely low and high pressure can influence selectivity, transformation efficiency, coking rate and/or speed of reaction unfriendly; Yet, still can form light olefin, for this reason, these pressure extremely are considered to a part of the present invention.

The WHSV of various oxygenate conversion reaction (be defined as the weight of total oxygenatedchemicals of reaction zone/hour/weight of molecular sieve in the catalyzer of reaction zone) can be used to implement the present invention.Total oxygenatedchemicals of reaction zone comprises all oxygenatedchemicalss in the liquid and vapor capacity.Though this catalyzer can contain other material as inert material, filler or binding agent, WHSV only uses the weight of the molecular sieve in the catalyzer of reaction zone to calculate.WHSV is enough to keep catalyzer to be fluidized ideally under reaction conditions and in reactor configuration and design.

Generally, WHSV is about 1 to about 5000hr ^-1, about ideally 2 to about 3000hr ^-1, most desirably about 5 to about 1500hr ^-1For the charging that comprises methyl alcohol, dme or their mixture, WHSV is about at least 20hr ideally ^-1, more desirably about 20 to about 300hr ^-1

The superficial gas velocity (SGV) of the raw material that comprises thinner and reaction product in reactor assembly preferably is enough to fluidisation molecular sieve catalyst composition in the reaction zone of reactor.In the method, especially in reactor assembly, more specifically the SGV in riser reactor is at least 0.1 meter per second (m/sec), preferably be higher than 0.5m/sec, more preferably be higher than 1m/sec, also more preferably be higher than 2m/sec, further preferably be higher than 3m/sec, most preferably be higher than 4m/sec.For example referring to the U.S. patent application serial number 09/708,753 of proposition on November 8th, 2000, the latter introduces for reference at this paper.

Fluid bed regenerator can close phase, turbulence or circulating fluidized bed (riser tube) mode are operated.Close phase or turbulence operating method are characterised in that close phase in bottom and top dilute phase, and run into when the superficial gas velocity of fluidizing agent is 0.01-2m/sec usually.Therefore solid is very good in the mixing of emulsion zone, has obtained in close suitable uniform temperature in mutually, even the oxidation of the carbon-containing sediment in revivifier is highly heat release.In the top dilute phase, the solid exchange is not so fast, and any thermopositive reaction that takes place in dilute phase will cause temperature to increase, when fluidizing agent is distinguished by this.

Fluid bed regenerator can also be operated with circulating fluidized bed or " riser tube " mode.This operator scheme is characterised in that the close of catalyzer flows in " riser tube " with regeneration gas, and separate solid and regeneration gas in the disengaging zone form dilute phase subsequently.In " riser tube " pattern, dilute phase can be the quiescent centre that is positioned at the riser tube outside, and wherein catalyzer separates by gravity, and perhaps it can carry out exporting in the tightly coupled cyclone separator with riser tube, and wherein catalyzer separates by centrifugal force.

No matter mode how, close is the place of wanting to take place the coke combustion reactions mutually, and dilute phase begins to form in the catalyzer district separated from the gas therein.

Secondary reaction can take place in dilute phase, causes temperature to be elevated to more than the medial temperature of close phase.These temperature difference lower by adding the CO oxidized metal.

Method of the present invention continues to be enough to form the time of required light olefin.Can obtain stable state or half stable state production during this period, this is largely by temperature of reaction, pressure, selected catalyzer, and the amount of recycled spent, regeneration degree, weight hourly space velocity, apparent velocity decides with other selected technological design characteristic.

The oxygenate rate should keep abundant height, to avoid industrial unacceptable charging recirculation level.Though 100% oxygenate rate is desirable for avoiding charging recirculation fully,, usually found the minimizing of unwanted by-products when transformation efficiency is about 98% or 98% when following.Because nearly about 50% of charging recirculation can be accepted industrial, is about 50 to about 98% so wish transformation efficiency.Many methods of using those of ordinary skills to be familiar with can remain on transformation efficiency this scope-50% to about 98%.Example comprises but is not necessarily limited to regulate one or more of following parameter: temperature of reaction; Pressure; Flow velocity (weight hourly space velocity and/or gas superficial flow velocity); Catalyst recycle speed; The reactor assembly configuration; Reactor configuration; Feed composition; Amount with respect to the liquid starting material of steam feed; The amount of catalyst recycle; The catalyst regeneration degree; Other parameter with the influence conversion.

Use the silicoaluminophosphamolecular molecular sieve catalyst composition with the preferred embodiment of oxygenate as the method for alkene in, this method is at 20hr at least ^-1WHSV and be lower than 0.016, preferably be less than or equal to the operation down of 0.01 temperature correction normalization method methane selectively (TCNMS).For example referring to U.S. patent No.5,952,538, the latter introduces for reference at this paper comprehensively.

Using molecular sieve catalyst composition be in another embodiment of method of one or more alkene with oxygenatedchemicals such as methanol conversion, and WHSV is at about 350-550 ℃ of silicon-dioxide and Me with 300-2500 ₂O ₃Be 0.01 to about 100hr under (Me is the IIIA or the VIII family element of the periodic table of elements) mol ratio ^-1For example referring to EP-0 642 485B1, the latter introduces for reference at this paper comprehensively.

Use molecular sieve catalyst composition that oxygenatedchemicals such as methanol conversion are described in (the average catalyst raw material at least 1.0 exposes the propane reduction under the rate to the open air) among the disclosed PCT WO 01/23500 on April 5 calendar year 2001 for other methods of one or more alkene, this application is introduced for reference at this paper.

From separation vessel, discharge coked molecular sieve catalyst composition, preferably, be incorporated in the regeneration system rapidly again by one or more cyclone separators.Regeneration system rapidly comprises wherein coking catalyst composition and regenerating medium, the revivifier that preferred oxygen-containing gas contacts under the general regeneration condition of temperature, pressure and the residence time.

The limiting examples of regenerating medium comprises oxygen, O ₃, SO ₃, N ₂O, NO, NO ₂, N ₂O ₅, air is with the air of nitrogen or carbonic acid gas dilution, oxygen and water (U.S. patent No.6,245,703), one or more of carbon monoxide and/or hydrogen.Regeneration condition is the coke from the coking catalyst composition to be burned to those of the level that preferably is lower than 0.5wt%, based on the gross weight of the coked molecular sieve catalyst composition that enters regeneration system rapidly.The coked molecular sieve catalyst composition of discharging from revivifier has formed regenerated molecular sieve catalyst composition.

Regeneration temperature is about 200 to about 1500 ℃, and preferably approximately 300 is to about 1000 ℃, and more preferably about 450 arrive about 750 ℃, most preferably about 550 to 700 ℃.Can use interchanger that the temperature in the revivifier is controlled to required scope.Regeneration pressure is that about 15psia (103kPaa) is to about 500psia (3448kPaa), preferably approximately 20psia (138kPaa) is to about 250psia (1724kPaa), more preferably approximately 25psia (172kPaa) is to about 150psia (1034kPaa), and most preferably approximately 30psia (207kPaa) arrives about 60psia (414kPaa).

The preferred residence time of molecular sieve catalyst composition in revivifier is about 1 minute to several hours, and most preferably about 1 minute to 100 minutes, the preferred amounts of oxygen in gas was about 0.01 to about 5mol%, based on the total amount of gas.

In one embodiment, with regeneration accelerator, typically metallic compound such as platinum, palladium etc. directly or indirectly join in the revivifier, for example with the coking catalyst composition.Also have, in another embodiment, as at U.S. patent No.6, described in 245,703, the fresh molecular sieve catalyst composition is joined in the revivifier of the regenerating medium that contains aerobic and water, this patent is introduced for reference at this paper comprehensively.

Be used in the metal that promotes carbon monoxide to be oxidized to carbonic acid gas under the catalyst regeneration condition in the present invention and be described in U.S. patent No.4, in 072,600 and 4,350,614 (Schwartz), full content is separately introduced for reference at this paper.These metals are the oxidation promotors that are selected from platinum, palladium, iridium, osmium, rhodium, ruthenium, rhenium and their mixture.This catalyst composition for example can comprise about 0.01 to about 100ppm (weight), about 0.01 arrives about 50ppm (weight) usually, and preferably approximately 0.01 is to about 5ppm (weight) oxidation promotor.

Similarly, U.S. patent No.4,151,112 people such as () Gladrow have described and have been used for coming the process of regenerated catalyst to promote carbon monoxide to be oxidized to the hydrocarbon conversion catalyst of carbonic acid gas by burning coke wherein, and this patent is introduced for reference at this paper.People such as Gladrow disclose be used for by burning in the presence of oxygen on it sedimentary coke come to promote under the condition of regeneration of spent catalyst that the CO burning is CO ₂Metal or its compound.Therefore, this catalyzer contains the 5th and 6 phases (Handbook of Chemistry and Physics, 38 of the VIII family that is selected from periodictable ^ThVersion, 1957), rhenium, one or more metals in chromium and the manganese, or their compound.The specific examples of these metals comprises platinum, palladium, rhenium, iridium, ruthenium, rhodium, osmium, manganese etc.Above-mentioned metal can also be with oxide compound, and the oxidation state of sulfide or other compound exists.These metals or compound comprise with being used to describe the present invention and therefore being suitable for term of the present invention " CO oxidized metal ".

For the present invention, " CO oxidized metal ", " CO ignition dope " and " CO oxidation promotor " is considered to equal term, comprises alloy and/or free metal.

The CO oxidized metal can join that to be used for oxygenate be the catalyzer of alkene in several modes.In one aspect of the invention, to in this procedure, the individual particles that contains the CO oxidized metal of contact catalyst be incorporated in the catalyst inventory by any convenience point, the CO oxidized metal be joined in the catalyzer indirectly thereby this CO oxidized metal of at least a portion transferred to wherein in this method.

This individual particles can comprise the inorganic porous oxide compound as carrier, comprises any porous material of being convenient to obtain such as aluminum oxide, boron oxide, silicon-dioxide, chromic oxide, magnesium oxide, zirconium white, titanium dioxide etc. and their mixture.These materials can also comprise one or more of various known clays, if you would take off stone, kaolin, halloysite, wilkinite, attapulgite etc.Preferably, inorganic porous oxide compound is one or more (Handbook of Chemistry and Physics, 38 of common siliceous class material of oxide compound of containing at least a metal of II-A, the III-A of periodictable of the silicon-dioxide of main amount and minor amount and IV-B family ^ThVersion, 1957).Representative materials comprises silica-alumina, silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-titania, silica-alumina-zirconium white, magnesium oxide etc.The most preferred inorganic porous oxide compound that is used as the carrier of CO oxidation promotor is an aluminum oxide.Most preferred inorganic porous oxide-base material is a silica-alumina.As everyone knows, these materials are generally prepared by the silica hydrogel or the water-sol, mix with aluminum oxide again, form to obtain required silica-alumina.Alumina content generally is about 5 to 40wt%, and preferred composition has about 10 to 35wt% alumina content.The numerous operations that are used to prepare silica-alumina have been described in the literature, U.S. patent Nos.2 for example, 908,635 and 2,844,523.

Preferably, the CO oxidized metal is joined in the granules of catalyst itself.Also more preferably, the CO oxidized metal is joined in the granules of catalyst, make the CO oxidized metal farthest be deposited on the granules of catalyst surface, simultaneously the deposition of CO oxidized metal on the internal void surface minimized.The latter can realize greater than the compound that contains the CO oxidized metal in the aperture on granules of catalyst surface by utilizing diameter.

The CO oxidized metal is incorporated in individual particles or the granules of catalyst as dipping and vapor deposition process by known technology.Preferably, introduce by one or more the solution impregnation particle of compound with the above-mentioned metal of the amount that is enough to provide desired concn the CO oxidized metal.For example, the aqueous solution of Palladous nitrate and/or Platinic chloride can contact with the porous inorganic oxide carrier, obtains slurry, after this can filter, and drying, calcining, and/or with hydrogen or other reducing gas prereduction that is fit to.Can also use the organic soluble compound of CO oxidized metal.For example, methyl ethyl diketone platinum Pt (AcAc) ₂Can be used for introducing the CO oxidized metal.This compound is especially effective, is stopped by many molecule sieve apertures because it is fully big.Gained supports the CO oxidation promotor and can calcine according to the known operation of those skilled in the art.

The CO oxidized metal is generally to be no more than 5% amount based on total catalyst weight, 1% the amount that for example is no more than based on total catalyst weight exists, promptly, to be no more than amount based on the 5000ppm of total catalyst weight, be no more than amount, or even surpass amount existence based on the 100ppm of total catalyst weight based on the 500ppm of total catalyst weight.

In another embodiment, wherein the CO oxidized metal is a VB family metal, vanadium for example, and this catalyzer contains 5000wppm at least, 5000-100000wppm for example, preferred 10000-50000wppmCO oxidized metal.

For one embodiment of the invention, wherein the CO oxidized metal is a platinum, and platinum exists with the amount based on the 0.1-10000ppm of total catalyst weight, and for example the CO oxidized metal is to exist with the amount based on the 1-5000ppm of total catalyst weight.

In one embodiment, part from the coked molecular sieve catalyst composition of revivifier directly turns back in one or more riser reactors, or by contacting in advance with raw material, or contact, or contact and return indirectly with regenerated molecular sieve catalyst composition or following cooling regenerated molecular sieve catalyst composition with the fresh molecular sieve catalyst composition.

The burning of coke is thermopositive reaction, in one embodiment, the temperature in the regeneration system rapidly is controlled by the various technology in this area, comprises cooling gas is added regenerator vessel, with intermittence, continuous or semicontinuous mode, or the combination of these modes is operated.Preferred technology comprises the catalyst cooler of discharging regenerated molecular sieve catalyst composition and this regenerated molecular sieve catalyst composition being fed formation refrigerative regenerated molecular sieve catalyst composition from regeneration system rapidly.In one embodiment, this catalyst cooler is to be positioned at the inner or outside interchanger of regeneration system rapidly.

In one embodiment, with continuous circulation the water cooler regenerated molecular sieve catalyst composition is turned back to revivifier, perhaps (referring to the U.S. patent application serial number 09/587 that proposed on June 6th, 2000,766), allow a part of refrigerative regenerated molecular sieve catalyst composition turn back to regenerator vessel with continuous circulation, and another part refrigerative regenerated molecular sieve catalyst composition directly or indirectly turns back to riser reactor, or the regenerated molecular sieve catalyst composition of a part or the by product in refrigerative regenerated molecular sieve catalyst composition and the gaseous effluent contact (disclosed PCT WO 00/49106 on August 24th, 2000), and above-mentioned document is all for reference in the comprehensive introducing of this paper.In another embodiment, as the U.S. patent application serial number 09/785 that proposes in February 16 calendar year 2001, described in 122, will with alcohol, preferred alcohol, the 1-propyl alcohol, the regenerated molecular sieve catalyst composition of 1-butanols or the contact of their mixture is incorporated in the reactor assembly, and this application is introduced for reference at this paper comprehensively.

Other method that is used to operate regeneration system rapidly is disclosed in U.S. patent No.6, and in 290,916 (controlling moisturies), the latter introduces for reference at this paper comprehensively.

Ideally, recirculation and (comprise molecular sieve and any other material such as binding agent with catalyzer that charging contacts again, filler etc., additional non-reacted solid) speed is oxygenatedchemicals to about 1 to about 100 times of the total feed rate of reactor, more desirably about 10 to about 80 times, most desirably about 10 to about 50 times.Ideally, with oxygenatedchemicals about 0.1 to about 10 times to the total feed rate of reactor, more desirably with about 0.2 to about 5 times, most desirably about 0.3 to about 3 times speed, and a part of discharging the catalyzer that comprises molecular sieve and any other material such as binding agent, filler etc. from reactor is used for regeneration and is recycled to reactor.It will be apparent to those skilled in that non-reacted solid can also be regenerated in the above described manner with catalyzer.

The preferred embodiment that is used for reactor assembly of the present invention is the circulating fluid bed reactor with cyclic regeneration, and is similar to modulation (modem) fluid catalystic cracking device.Fluidized-bed is unpractical for this method, because oxygenatedchemicals to conversion of olefines is high heat release method, this need have the several stages of side cooler or other cooling apparatus.This reaction is because the production of low pressure, low density gas has also caused high pressure drop.

Because the necessary frequent regeneration of catalyzer can be rejected to a part of catalyzer in the revivifier easily so reactor should make, there catalyzer contact regenerating medium, preferably contain aerobic, most preferably the gas of air to burnout from the coke of catalyzer, recovers catalyst activity like this.Should select the condition of temperature, oxygen partial pressure and the residence time in the revivifier,, preferably be lower than the coke content on the regenerated catalyst of about 0.5wt% so that obtain to be lower than about 2wt%.At least a portion regenerated catalyst should turn back in the reactor.

Importantly, reactor so that the coke of high relatively average content-be higher than about 1.5wt%, preferably approximately 2 to about 30wt%, the mode of most preferably about amount of 2 to about 20wt%-be retained in the reactor designs.If reactor is high-velocity fluidized bed reactor (being sometimes referred to as riser reactor), the part of the catalyzer of discharging from reactor head must turn back to Reactor inlet so.This is different from typical fluidized-bed cat cracker (FCC) riser reactor, and wherein whole or most catalyzer of discharging from reactor head is transported to revivifier.Coking catalyst directly turns back to reactor, and no longer the method for the green coke catalyzer average coke level in the reactor that makes runs up to preferred levels.By regulating the throughput ratio of the coking catalyst between revivifier and the reactor, can keep preferred coking level, or " required carbon-containing sediment ".

If design has low gas flow rate ('s approximately below the 2m/sec) fluidized-bed reactor, can use cyclone separator that catalyst fines is turned back to fluidized bed reaction zone so.These reactors generally have the high solid recirculation rate in fluidized-bed, this makes the coke level on the catalyzer be increased to preferred levels.

For the coke content in assaying reaction device and the revivifier, can each position from recirculation system regularly extract the little amount of catalyst sample and be used to measure carbon content.Thereby can the conditioned reaction parameter.

From regeneration system rapidly, preferably regenerated molecular sieve catalyst composition and fresh molecular sieve catalyst composition and/or egr molecule sieve catalyst composition and/or raw material and/or the live gas or the liquid merging of discharging from catalyst cooler turns back to riser reactor again.In another embodiment, the regenerated molecular sieve catalyst composition of discharging from regeneration system rapidly directly turns back to riser reactor, chooses wantonly after passing through catalyst cooler.In another embodiment, semicontinuous or successive carrier, as rare gas element, raw material steam, steam or analogue promote that regenerated molecular sieve catalyst composition is incorporated into reactor assembly, in preferred one or more riser reactors.

In one embodiment, the optimal coke content on the molecular sieve catalyst composition in reaction zone keeps by control regenerated molecular sieve catalyst composition or the flow velocity of refrigerative regenerated molecular sieve catalyst composition from the regeneration system rapidly to the reactor assembly.At Michael Louge, Experimental Techniques, Circulating Fluidized Beds, Grace, Avidan and Knowlton, eds., Blackie, described many technology of the flow velocity that is used to control molecular sieve catalyst composition among 1997 (336-337), the document is introduced for reference in this article.This is called as the holomorphosis mode.In another embodiment, the optimum content of the coke on the molecular sieve catalyst composition in reaction zone keeps by the flow velocity that control flow into the oxygen-containing gas of revivifier.This is called as the partial regeneration mode.

Coke content on molecular sieve catalyst composition is by getting molecular sieve catalyst composition and measuring its carbon content and measure at certain point of method for transformation.The typical content of the coke on the molecular sieve catalyst composition after regeneration is 0.01 to about 15wt%, preferably approximately 0.1 to about 10wt%, more preferably about 0.2 to about 5wt%, most preferably about 0.3 to about 2wt%, based on the gross weight of molecular sieve, but not the gross weight of molecular sieve catalyst composition.

In a preferred embodiment, molecular sieve catalyst composition in the reaction zone contains about 1 to about 50wt%, preferably approximately 2 to 30wt%, more preferably about 2 to about 20wt%, most preferably about 2 to about 10wt% coke or carbon-containing sediment, based on the gross weight of the mixture of molecular sieve catalyst composition.For example referring to U.S. patent No.6,023,005, this patent is introduced for reference at this paper comprehensively.Should be realized that the molecular sieve catalyst composition in the reaction zone is made up of regenerated catalyst and the mixture of catalysts with carbon-containing sediment of certain limit content.Therefore the mensuration content of carbon-containing sediment represent the average content of single granules of catalyst.

Discharge gaseous effluent from separation system, enter recovery system again.Have and manyly knownly can be used for separating alkene and recovery system, technology and the program of purification alkene from gaseous effluent.Recovery system generally comprises the one or more or binding substances in various separation, fractionation and/or distillation tower, post, splitter or the unit, reactive system such as ethylbenzene production systems (U.S. patent No.5,476,978) and other deriving method such as aldehyde, ketone and ester production system (U.S. patent No.5,675,041), and Other related equipment, for example various condensers, interchanger, refrigeration system or cooling unit, compressor, knockout drum or still, pump etc.

These separately or the limiting examples of the tower, post, splitter or the unit that are used in combination comprise demethanizing tower, preferred high temperature demethanizing tower, deethanizing column, depropanizing tower, preferred wet method depropanizing tower, washing tower (usually being called as soda-wash tower) and/or quench tower, resorber, adsorber, film, ethene (C2) splitter, propylene (C3) splitter, one or more in butylene (C4) splitter etc.

Can be used for mainly reclaiming alkene, preferred main alkene or light olefin such as ethene, the various recovery systems of propylene and/or butylene are described in U.S. patent No.5,960,643 (secondary ethylene-rich materials flows), U.S. patent Nos.5,019,143,5,452,581 and 5,082,481 (membrane sepn), U.S. patent No.5,672,197 (pressure dependency sorbent materials), U.S. patent No.6,069,288 (hydrogen removals), U.S. patent No.5,904,880 (one step of recovery methyl alcohol is converted into hydrogen and carbonic acid gas), U.S. patent No.5,927,063 (reclaiming methyl alcohol) to GTPU (Gas Turbine Power Unit), U.S. patent No.6,121,504 (directly product quenchings), U.S. patent No.6,121,503 (without the high purity olefin of superfractionation), and U.S. patent No.6,293, in 998 (the transformation absorption), all these patents are introduced for reference at this paper comprehensively.

Usually, what follow with most of recovery systems is other product that exists with preferred principal product, the generation of by product and/or pollutent or accumulation.Preferred principal product light olefin typically is purified as ethene and propylene and is used to derive production method such as polymerization process.Therefore, in the most preferred embodiment of recovery system, recovery system also comprises purification system.For example, especially the light olefin of producing in the MTO method enters purification system, removes the by product or the pollutent of low levels.

The limiting examples of pollutent and by product generally comprises polar compound such as water, alcohols, carboxylic acid, ethers, oxycarbide class, sulphur compound such as hydrogen sulfide, carbonyl sulfide and thio-alcohol, ammonia and other nitrogen compound, arsenic, phosphine and muriate.Other pollutent or by product comprise hydrogen and hydro carbons such as acetylene, methylacetylene, propadiene, divinyl and butine.

Other recovery system that comprises purification system (for example being used for purifying alkene) is described in Kirk-Othmer Encyclopedia of Chemical Technology, and the 4th edition, the 9th volume, John Wiley ﹠amp; Sons, 1996, in 249-271 page or leaf and the 894-899 page or leaf, the document is introduced for reference at this paper.Purification system also is described in for example U.S. patent No.6,271,428 (purifying of diene-hydrocarbon flow), U.S. patent No.6, the U.S. patent application No.09/689 that 293,999 (separation of propylene and propane) and on October 20th, 2000 propose, in 363 (the using the purging materials flow of hydration catalyst), these documents are introduced for reference at this paper.

Typically, being to have in the alkene of 2 or 3 carbon atoms with one or more oxygenate, form or produced a certain amount of hydro carbons, alkene especially more specifically has alkene and other by product of 4 or 4 above carbon atoms.In recovery system of the present invention, comprised and be used to transform product that contains in the emission gases of discharging or the reactive system that transforms those products that produce owing to used recovery system from reactor.

In one embodiment, the emission gases of discharging from reactor feeds recovery system, forms one or more flow containing hydrocarbons, especially contains 〉=hydrocarbon (C of 3 carbon atoms ₃ ⁺) materials flow.In this embodiment, will contain C ₃ ⁺The materials flow of hydrocarbon feeds first fractionation zone, forms thick C ₃Hydrocarbon and contain C ₄ ⁺The materials flow of hydrocarbon contains C ₄ ⁺The materials flow of hydrocarbon feeds the after-fractionating district, forms thick C ₄Hydrocarbon and contain C ₅ ⁺The materials flow of hydrocarbon.The above hydrocarbon of 4 carbon or 4 carbon comprises butylene class such as 1-butylene and 2-butylene, butadiene type, saturated butanes class and isobutyl alkanes.

Method of the present invention is comprising entrance region ideally, carries out in the reactor assembly of reaction zone and disengaging zone.When carrying out in the reactor assembly of method of the present invention in the type, the catalyzer/solid of at least a portion is recycled to entrance region from the disengaging zone, thereby keeps reactor near under the isothermal condition.The steam feed of at least a portion mixes at entrance region with catalyzer/solid then, enters reaction zone again, carries out oxygenatedchemicals there to olefin reaction.Randomly, the thinner of liquid feeding and/or combined feed total feed part or its various subdivisions can enter one or more positions of entrance region and/or reaction zone.Use this device, catalyzer/solid can be in reactor assembly inside or the reactor assembly external recirculation, when catalyzer/solid is recycled to entrance region and/or reaction zone from the disengaging zone.As described in also, the catalyzer/solid of other parts can be chosen wantonly and remove from reactor assembly and be transported to revivifier, with regenerated catalyst.Catalyzer/solid from revivifier can turn back in any one of these three districts, maybe can enter the conduit that is used for catalyzer/solid is recycled to from the disengaging zone entrance region or reaction zone.

The embodiment that can be used for reactor assembly of the present invention is expressed as 300 generally in Fig. 1.Oxygenatedchemicals 303 can be by evaporating pre-treatment to small part in preheater.Methanol feeding mixes in entrance region 304 in the bottom of riser reactor 306 with catalyzer from pipeline 327, this catalyzer comprise with valve 330 regulate from not regeneration (coking) catalyzer of pipeline 324 and/or the regenerated catalyst of regulating by valve 415 from pipeline 412.Rare gas element and/or steam 403 can be used for diluting oxygenatedchemicals, promote catalyst stream and the table pipeline that keep-ups pressure does not have catalyzer.This rare gas element and/or steam can mix in the reactor 306 of a plurality of positions 309 monitoring in its temperature with oxygenatedchemicals and catalyzer.This reaction is heat release, and preferred temperature of reaction (about 300 ℃ to about 500 ℃) keeps by heat extraction.Can come heat extraction by any suitable mode, comprise but be not necessarily limited to and use catalyst cooler 406 cooling reactors, feeding is cooled to the catalyst charge of reactor as some methyl alcohol of liquid, or the arbitrary combination of these methods.

The reactor effluent that contains product, coking catalyst, thinner and unconverted raw material should flow into disengaging zone 312.In this disengaging zone, from gas material, isolate coking catalyst, the cyclonic separator that this gas material utilizes gravity and/or has dipping

tube

318 and 321 is discharged from pipeline 345.Part coking catalyst turns back to Reactor inlet by the pipeline 324 with valve 330 controls.That part of coking catalyst of the regenerated of wanting at first be transported to stripping zone 333, use steam or other rare gas element to come from catalyzer to reclaim the hydro carbons of absorption there.Stripped useless coking catalyst should flow into regeneration container 401 via the pipeline 339 with valve 342 controls.Be transported to regeneration container 401 that part of catalyzer should with the regenerating medium of introducing by bottom revivifier import, the gas that preferably contains aerobic, for example air contacts to temperature, pressure and the residence time of the level that is lower than about 0.5wt% the aforesaid coke of catalyzer can being burnouted.Preferred temperature in the regeneration container is about 550 to about 700 ℃, and the preferred oxygen concentration in leaving the gas of revivifier is about 0.1 to about 5vol.%, and the preferred residence time is about 1 to about 100 minutes.

Burnouting of coke is heat release.Temperature can remain on proper level by any acceptable method, including, but not limited to adding cooling gas, and with the catalyzer in the catalyst cooler 406 cooling regeneration container, or the combination of these methods.

Via the

pipeline

409 and 412 with valve 415 control this regenerated catalyst is transported to reactor 306, it mixes in pipeline 327 with recirculation coking catalyst from pipeline 324 there, and oxygenate feedstock final and from pipeline 303 mixes.This regenerated catalyst can utilize the rare gas element of introducing by lift gas pipeline 403, and steam or methanol vapor rise to reactor 306.This method repeats voluntarily in continuous or semicontinuous mode.Cooling heat reactor product gas, condensation and collection water by product, and reclaim required olefin product gas, be used for further processing.

For the level of the coke in assaying reaction device and the revivifier, can regularly take the little amount of catalyst sample away from a plurality of positions of recirculation system, be used to measure carbon content.In view of the above can the conditioned reaction parameter.

General experiment operation

MTO reaction test and GC analyze

Unless otherwise prescribed, methanol-to-olefins (MTO) conversion reaction is at 2.5WHSV, carries out in tubular type microfluidic reactor under 450 ℃ and the 276KPa (40psia).External diameter 0.25 ", the reactor of length 8 " and thickness 0.04 " is made by silicon steel.

Discharge from tubular reactor is collected in the Valco sampling valve with 15250,1 sample loop.The effluent samples of collecting is analyzed by the on-line gas chromatography (Hewlett Packard 6890) that flame ionization detector is housed.Used chromatographic column is 150m, 0.25mm (internal diameter) fused silica capillary column (Model No.Petrocol DH 150).

Effusive discharge by above-mentioned sampling valve be used to remove the separating after the hydrazine of liquid such as water and methyl alcohol, gas-phase product is also collected in stainless steel cylinder.

The selectivity of reporting in table (wt%) data are transformation efficiency weighted mean (weighedaverage), calculate according to the product of discharging from reactor.In other words, water and coke do not comprise as product in these calculate.The C that in table, enumerates ₁, C ₂ ⁼, C ₂ ^o, C ₃ ⁼, C ₃ ^oAnd C ₄ ⁼Difference nail alkane, ethene, ethane, propylene, propane and butylene class.

The oxidation of programmable temperature (TPO)

Use TPO (oxidation of programmable temperature) measures the carbon amount in the coke removal experimentation.TPO is undertaken by the MTO catalyzer (5.2wt% carbon, 37.9wt%SAPO-34 and 56.9wt% clay bond) that adds 5-10mg in quartz reactor.Speed with 63ml/min will contain 1%O in helium ₂Carrier gas be incorporated in the quartz reactor.Heat this reactor with 13 ℃/minute constant rate of speeds.Expellant gas enters methanator from quartz reactor, and it contains ruthenium catalyst.This catalyzer under 400 ℃ with CO and CO ₂Be converted into methane.The methane of being produced uses flame ionization detector (FID) to measure continuously.For the CO that is determined in the TPO experimentation generates, use the carbon dioxide trap of filling soda-asbestos (solid of sodium hydroxide dipping), before being transported to methanator, from discharge gas, remove CO fully ₂Therefore, the TPO signal (FID) that obtains with the soda-asbestos trap has ad hoc been measured the amount by the carbon CO that oxidation generates on catalyzer.The details of this technology can be at S.C.Fung and C.A.Querini, J.Cat., and 138,240 (1992) and C.A.Querini and S.C.Fung, J.Cat. finds in 141,389 (1993), and described document is introduced for reference at this paper.

The wet impregnation of platinum on SAPO-34

Use wet impregnation that Pt is loaded on the SAPO-34 catalyzer and within.In the Preparation of catalysts that has loaded 5000wppm (weight PPM) Pt, with 0.013g methyl ethyl diketone platinum or Pt (AcAc) ₂(99.9%, Aldrich) be dissolved in the 2.2ml toluene.The consumption of toluene is enough to the mesopore and the macropore volume of catalyst filling.This drips of solution is added to going among the template SAPO-34 of 1.0028g.This wet mixture in vacuum drying oven dry 1 hour is to remove toluene.The gained solid catalyst was calcined 2 hours down at 350 ℃ in stove then.Platinum concentration in the catalyzer of preparation is like this determined by ultimate analysis.Two kinds of SAPO-34 catalyzer that contain 2000wppm Pt and 5000wppm Pt have respectively been prepared according to this operation.Shown that in embodiment 3-5 Pt optionally influences the effectiveness of SAPO-34 catalyzer in promoting the CO oxidation of flooding with these Pt to MTO.

Under 510 ℃, by in flow reactor, flowing into H with the He dilution ₂Air-flow (10ml/min H ₂With 40ml/min He) reach 2 hours and carry out the Pt reduction.Oxidation is at O ₂Under 600 ℃, carried out 2 hours in the air-flow (50ml/min).

Hydrogenation absorption

Use hydrogenation absorption to measure the dispersion or on the contrary of Pt particle in the SAPO-34 that FCC CO promotor (promotercatalyst) and Pt flood, agglomerant degree.The hydrogenation determining adsorption how many hydrogen atoms be present in Pt total atom number absorption on the catalyzer.When the H/Pt atomic ratio was 1, all the Pt atoms in catalyzer can be utilized by hydrogen atom, that is, the Pt particle is very little, approximately less than 10 .When the H/Pt＞0.7, support the Pt particle and it is said high dispersing, when H/Pt is 0.1-0.7, be the moderate dispersive.It is low supporting that the Pt particulate disperses, when H/Pt＜0.1.The details of analytical technology can be at Structure ofMetallic Catalyst, J.R.Anderson, and the 6th chapter, the 295th page, AcademicPress finds in (1975).

Embodiment 1

To contain 780wppm Pt/Al ₂O ₃The FCCCO promotor that is purchased of (780wppm Pt is on aluminum oxide) joins in the MTO catalyzer, and the latter is contained 7.2wt% carbon, 37.1wt%SAPO-34 and 55.7wt% clay bond.The granularity of MTO catalyzer is about 100 microns.By (Intercat COP-850) joins to prepare in the MTO catalyzer and contains 7.8wppm respectively, 39.0wppm, four kinds of catalyzer of 156wppm and 312wppm Pt with an amount of FCC CO promotor.Table 1 has shown the effect of interpolation CO promotor for MTO selectivity of catalyst (wt%).

Table 1

Pt wppm	C ₁ Wt％	C ₂ ^＝ Wt％	C ₂ ^o Wt％	C ₃ ^＝ Wt％	C ₃ ^o Wt％	C ₄ ^＝ Wt％	C ₂ ^＝+C ₃ ^＝ Wt％
Pt wppm	C ₁ Wt％	C ₂ ^＝ Wt％	C ₂ ^o Wt％	C ₃ ^＝ Wt％	C ₃ ^o Wt％	C ₄ ^＝ Wt％	C ₂ ^＝+C ₃ ^＝ Wt％	0	1.7	35.2	1.0	43.2	2.0	13.0	78.4
7.8	2.0	35.5	1.2	42.7	2.0	12.7	78.2	0	1.7	35.2	1.0	43.2	2.0	13.0	78.4
7.8	2.0	35.5	1.2	42.7	2.0	12.7	78.2	39	3.4	32.8	4.7	40.2	2.8	12.4	73.0
156	9.0	11.1	26.5	28.6	10.8	10.9	39.7	39	3.4	32.8	4.7	40.2	2.8	12.4	73.0
156	9.0	11.1	26.5	28.6	10.8	10.9	39.7	312	13.5	1.9	35.0	18.2	18.9	9.7	20.1

Data presentation in the table 1 has minimum influence for main olefine selective under low Pt concentration.For example, under the Pt of 7.8wppm carrying capacity, for C ₃ ⁼The selectivity 0.5wt% that only descends, and increase 0.3wt% for selectivity of ethylene.

When increasing Pt concentration by the amount that increases the FCC CO promotor in the mixture, the data presentation in the table 1 to ethene and optionally significant adverse influence of propylene, for example, 5.4wt% descends under 39wppm Pt.

Therefore, the amount that joins the FCC CO promotor in the MTO reactor need accurately be controlled under the level that does not cause ethene and the influence of propylene selectivity significant adverse.

Embodiment 2

Use in TPO research and contain 5.2wt% carbon, the MTO catalyzer of 37.9wt%SAPO-34 and 56.9wt% clay bond is to investigate FCC CO promotor at CO to CO ₂Oxidation in effectiveness.An amount of FCC CO promotor (IntercatCOP-850) is joined in the MTO catalyzer, make that the Pt concentration in final mixture is 18.8wppm.With with carry out TPO experiment without the soda-asbestos trap so that measure CO and CO ₂Table 2 shown with or without the MTO catalyzer of FCC CO promotor as CO and CO ₂The carbon wt% that emits.

Table 2

Pt wppm	The carbon wt% that emits as CO	As CO ₂The carbon wt% that emits	Total carbon wt%
Pt wppm	The carbon wt% that emits as CO	As CO ₂The carbon wt% that emits	Total carbon wt%	0	3.3	1.9	5.2
18.8	0.2	5.0	5.2	0	3.3	1.9	5.2

The TPO data presentation, the existence of 18.8wppm Pt greatly reduces the CO signal.The total amount of the CO that is generated is equivalent to 0.2wt% carbon, reduces by 94%.This shows that the existence of Pt has promoted CO to be oxidized to CO ₂

Embodiment 3

Prepare two kinds of platiniferous catalyzer by wet impregnation according to the operation of in above general experiment operation, describing in detail.The Pt concentration of these two kinds of catalyzer is respectively 2000wppm and 5000wppm.Table 3 has compared and has been used for the selectivity of catalyst data that contain 5000wppm Pt and the selective data that do not load the parent SAPO-34 of Pt of methyl alcohol to olefin reaction.MTO is reflected at 450 ℃, carries out under 276KPa (40psia) and the 25WHSV.

Table 3

Pt wppm	C ₁ Wt％	C ₂ ^＝ Wt％	C ₂ ^o Wt％	C ₃ ^＝ Wt％	C ₃ ^o Wt％	C ₄ ^＝ Wt％	C ₂ ^＝+C ₃ ^＝ Wt％
Pt wppm	C ₁ Wt％	C ₂ ^＝ Wt％	C ₂ ^o Wt％	C ₃ ^＝ Wt％	C ₃ ^o Wt％	C ₄ ^＝ Wt％	C ₂ ^＝+C ₃ ^＝ Wt％	0	1.0	28.2	1.2	38.6	7.1	17.5	66.8
5000	1.1	28.0	2.4	39.0	7.0	16.9	67.0	0	1.0	28.2	1.2	38.6	7.1	17.5	66.8

Notice that 5000wppm Pt wet impregnation does not have the influence of demonstration to the SAPO-34 catalyst performance in SAPO-34.In order to contrast, when Pt introduced with the form of FCC CO promotor, the Pt concentration of 39wppm had shown ethene and optionally remarkably influenced of propylene (embodiment 1, table 1).

Because the granularity of methyl ethyl diketone platinum is obviously greater than the aperture of SAPO-34 molecular sieve, so methyl ethyl diketone platinum great majority are on the outside surface of SAPO-34 crystallite.Pt is not a high dispersing, because the outside surface of SAPO-34 crystallite only is the sub-fraction of its total area, its most of surface-area are the surface-area in crystals hole.Shown in embodiment 4, can use hydrogenation absorption to measure Pt and disperse.

Embodiment 4

The dispersion of hydrogenation determining adsorption Pt particle in the SAPO-34 catalyzer of FCC CO promotor and Pt dipping.It is adsorbed that hydrogenation absorption has recorded the Pt total atom number how many hydrogen atoms are present on the catalyzer.When the H/Pt atomic ratio was 1, all the Pt atoms in catalyzer can be utilized by hydrogen atom, that is, the Pt particle is very little, approximately less than 10 .Table 4 shows that the H/Pt ratio of FCC CO promotor is 0.90, and the Pt atom of indication 90% is that the SAPO-34 of surface atom (little Pt granularity) and Pt dipping has shown 0.01 low H/Pt, indicate big Pt granularity, and only 1% Pt atom is a surface atom.

Table 4

The Pt catalyzer	Pt(wppm)	H/Pt
The Pt catalyzer	Pt(wppm)	H/Pt	FCC CO promotor	780	0.9
The SAPO-34 of Pt dipping	2000	0.01	FCC CO promotor	780	0.9

Embodiment 5

The catalyzer of Pt dipping reduced and oxidation in the flow reactor of laboratory before MTO test reaction, to simulate reducing environment in reaction zone and the well-oxygenated environment in revivifier respectively.Table 5 has shown the SAPO-34 selectivity of catalyst data with 2000wppm Pt dipping.

Table 5

Pt wppm	Handle	C ₁ Wt％	C ₂ ^＝ Wt％	C ₂ ^o Wt％	C ₃ ^＝ Wt％	C ₃ ^o Wt％	C ₄ ^＝ Wt％	C ₂ ^＝+C ₃ ^＝ Wt％
Pt wppm	Handle	C ₁ Wt％	C ₂ ^＝ Wt％	C ₂ ^o Wt％	C ₃ ^＝ Wt％	C ₃ ^o Wt％	C ₄ ^＝ Wt％	C ₂ ^＝+C ₃ ^＝ Wt％	0	Do not have	0.8	33.1	0.8	42.5	2.9	15.3	75.6
2000	Do not have	0.8	32.2	0.8	43.3	3.2	15.4	75.5	0	Do not have	0.8	33.1	0.8	42.5	2.9	15.3	75.6
2000	Do not have	0.8	32.2	0.8	43.3	3.2	15.4	75.5	2000	Reduction	1.2	32.7	1.7	42.9	4.0	14.1	75.6
2000	Oxidation	1.0	33.7	1.1	42.6	4.0	14.0	76.3	2000	Reduction	1.2	32.7	1.7	42.9	4.0	14.1	75.6

Though C ₁-C ₃ ^oAs if the selective paraffin appropriateness increase, but the not loss of the selectivity of ethene after simulation reaction/reprocessing cycle and propylene.

Embodiment 6

Promoting that by the SAPO-34 that uses TPO to study the Pt dipping CO is oxidized to CO ₂Reaction in effectiveness.Prepare the sample that contains Pt and carbon that is used for TPO research by the SAPO-34 that mixes an amount of MTO catalyzer that contains coke and Pt dipping.Two kinds of samples that prepare Pt concentration so respectively by the SAPO-34 of 2000wppm and 5000wppm Pt dipping with 48wppm and 121wppm.The carbon content of two kinds of samples is 5.2wt%.Table 6 has shown the TPO data of these two kinds of samples and the TPO data that do not have the sample of Pt.

Table 6

Pt wppm	The carbon wt% that emits as CO	As CO ₂The carbon wt% that emits	Total carbon wt%
Pt wppm	The carbon wt% that emits as CO	As CO ₂The carbon wt% that emits	Total carbon wt%	0	3.3	1.9	5.2
48	0.2	5.0	5.2	0	3.3	1.9	5.2
48	0.2	5.0	5.2	121	0.2	5.0	5.2

Though the Pt dispersity of the SAPO-34 catalyzer of these Pt dippings is low, they can be converted into CO with CO very effectively under the Pt concentration suitable with high dispersive FCC CO promotor ₂

Therefore, as if the catalyzer of being correlated with when the carbon monoxide oxidized metal is disperseed by appropriateness or is hanging down under the dispersity (for example when the wet impregnation by methyl ethyl diketone platinum adds the carbon monoxide oxidized metal), and it can equally with industrial FCC CO promotor be converted into CO with CO effectively in the revivifier of oxygenate to olefin ₂, and do not have the influence of demonstration for the SAPO-34 catalyst performance, that is, ethene and propylene selectivity be loss not.

Embodiment 7

In oxygenate conversion reaction method of the present invention, use and the described similar fluidized bed reactor arrangement of Fig. 1.Therefore, some catalyzer flow into regeneration container 401 and turn back to entrance region 304 therefrom from catalyst stripping equipment 333, and some pipelines 324 and turn back to entrance region 304 of flowing through are not regenerated.This device is used for studying and will joins the response of the reactor and the revivifier of MTO catalyzer at the identical FCC of the being purchased CO ignition dope (combustion promoter catalyst) described in the embodiment 1.

Before adding the CO combustion improver, rare disengaging zone, the top of revivifier is usually moved under the temperature higher than regenerator bed temperature.Termly, the head experience of revivifier is quick, and partial sometimes temperature raises.Fig. 2 shows the revivifier head thermopair that the experience fast temperature raises in routine or stable condition.Catalyst coke carrying capacity with 0.8wt% in revivifier has obtained in the data shown in Fig. 2.After obtaining these data, FCC CO ignition dope and MTO catalyzer physical mixed under the cocatalyst concentration of 830wppm.When promotor is 780wppm Pt/Al ₂O ₃The time, the total concn of Pt in recycling catalyst is 0.65wppm.Fig. 3 proves, adds promotor and has eliminated regular elevated temperature excursions.Catalyst coke carrying capacity with 0.8wt% in revivifier has also obtained these data.

The interpolation of promotor does not have the conversion of disadvantageous effect oxygenatedchemicals to light olefin.In device shown in Figure 1, methyl alcohol is with 450 ℃ average riser temperature, 24-25hr ^-1Space velocity and the reactor catalyst coke carrying capacity of 7.0wt% under 25psig, add.In two kinds of examples, will be at first 0 and then 0.65wppm Pt join in the recycling catalyst.Come self-reacting product in table 7, to enumerate.CO, CO ₂And H ₂Quantitative analysis show that these materials are not subjected to the influence of the 0.65wppm Pt in recycling catalyst.

Table 7

		Example 1	Example 2
		Example 1	Example 2	Pt concentration	ppmw	0	0.65
Pressure	psig	25	25	Pt concentration	ppmw	0	0.65
Pressure	psig	25	25	The Rxr temperature	℃	450	450
The Rgn temperature	℃	677	677	The Rxr temperature	℃	450	450
The Rgn temperature	℃	677	677	The Rxr coke	wt％	7.0	7.0
Sp speed	hr ^-1	24.7	24.1	The Rxr coke	wt％	7.0	7.0
Sp speed	hr ^-1	24.7	24.1	Transformation efficiency	wt％	91.7	90.1
C ₁	wt％	0.826	0.841	Transformation efficiency	wt％	91.7	90.1
C ₁	wt％	0.826	0.841	C ₂ ^＝	wt％	33.7	33.4
C ₂ ^o	wt％	0.596	0.578	C ₂ ^＝	wt％	33.7	33.4
C ₂ ^o	wt％	0.596	0.578	C ₃ ^＝	wt％	42.5	42.3
C ₃ ^o	wt％	1.99	1.90	C ₃ ^＝	wt％	42.5	42.3
C ₃ ^o	wt％	1.99	1.90	C ₄ ^＝	wt％	12.7	13.0
C ₅ ⁺	wt％	4.41	4.38	C ₄ ^＝	wt％	12.7	13.0
C ₅ ⁺	wt％	4.41	4.38	Coke	wt％	3.29	3.53

Using the Pt catalyzer in the MTO revivifier is that it provides effective CO to CO in the MTO revivifier as the advantage of CO promotor ₂Conversion and do not influence ethene and propylene selectivity simultaneously unfriendly, when in the MTO reactor, using.

Those of ordinary skill in the art will appreciate that, under situation without departing from the spirit and scope of the present invention, can make many changes to the present invention.Embodiment as herein described only is exemplary, is not used for limiting the present invention, and the present invention limits with following claims.

Claims

1, prepare the method for olefin product by oxygen-containing compound material, comprising:

A) allow raw material in reaction zone with comprise i) have less than the catalyzer of the molecular sieve of 5  bore size and ii) CO oxidized metal temperature and under the pressure of 100MPa, contact with 0.1kPa at 200 ℃ to 1000 ℃, thereby with feedstock conversion for comprising C ₂-C ₃The olefin product materials flow of alkene and on catalyzer, form carbon-containing sediment so that carbon-contained catalyst to be provided;

B) allow at least a portion and the regenerating medium that comprises oxygen of this carbon-contained catalyst comprise that having close fluid contacts mutually with in the breeding blanket of the fluid bed regenerator of rare fluid phase under 250 ℃ to 750 ℃ temperature, thereby obtain regenerated catalyst portion;

D) repeating step a)-c);

Wherein said CO oxidized metal exists with the amount based on the 0.01-100ppm of catalyst weight, and is not higher than 100 ℃ in the close phase of revivifier and the difference of the temperature between the dilute phase in step b).

2, the process of claim 1 wherein that the coke level on the catalyzer in the reactor is 2-30wt%.

3, the method for claim 2, wherein reactor is the high-velocity fluidized bed reactor, and a part of carbon-contained catalyst that leaves reactor turns back to reactor inlet.

4, the process of claim 1 wherein that regenerated catalyst portion has the carbon-containing sediment that is less than 5.0wt%.

5, the process of claim 1 wherein that regenerated catalyst portion has the carbon-containing sediment that is less than 3wt%.

6, the process of claim 1 wherein that regenerated catalyst portion has the carbon-containing sediment that is less than 1wt%.

7, the process of claim 1 wherein that described carbon-contained catalyst has the carbon-containing sediment that is no less than 5wt%.

8, the process of claim 1 wherein that described carbon-contained catalyst has the carbon-containing sediment that is no less than 3wt%.

9, the process of claim 1 wherein that described carbon-contained catalyst has the carbon-containing sediment that is no less than 1wt%.

10, the process of claim 1 wherein that described CO oxidized metal is to be selected from VB family, group vib, the element in VIIB family and the VIII family metal.

11, the method for claim 10, wherein said VB family metal is V; Described group vib metal is selected from Cr, Mo and W; Described VIIB family metal is Mn; And described VIII family metal is selected from Ni, Ru, Rh, Pd, Os, Ir and Pt.

12, the process of claim 1 wherein that described CO oxidized metal is Pt.

13, the process of claim 1 wherein that described CO oxidized metal is with the form interpolation of outside dimension greater than the opening diameter of described molecular sieve.

14, the process of claim 1 wherein that described CO oxidized metal adds with the form of methyl ethyl diketone platinum.

15, the process of claim 1 wherein that this molecular sieve catalyst has at least a framework of molecular sieve type that is selected from following group: AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG and THO.

16, the process of claim 1 wherein that this molecular sieve catalyst has the erionite of being selected from and chabazite, SAPO-34, at least a molecular sieve among SAPO-17 and the SAPO-18.

17, the process of claim 1 wherein to the selectivity of ethene and propylene with compare in the control methods that does not have to carry out in the presence of the described CO oxidized metal differ be no more than ± 5%.

18, the process of claim 1 wherein and compare, the selectivity % of ethene and propylene is not reduced with the same procedure of under the situation that does not have described CO oxidized metal, carrying out.

19, the process of claim 1 wherein described CO oxidized metal and described catalyzer are separated adding.

20, the process of claim 1 wherein and described CO oxidized metal is added by described breeding blanket.

21, the process of claim 1 wherein and described CO oxidized metal is added by described reaction zone.

22, the process of claim 1 wherein and described CO oxidized metal is joined in the catalyzer by ion-exchange.

23, the process of claim 1 wherein and keep 500-750 ℃ temperature in mutually at the close fluid of described revivifier.

24, the method for claim 12, the dispersity that wherein is added to the described CO oxidized metal in this system is the H:Pt of 0.01-0.7.